CN104779381A - Secondary battery, battery pack, electric vehicle, power storage system, power tool, and electronic device - Google Patents

Secondary battery, battery pack, electric vehicle, power storage system, power tool, and electronic device Download PDF

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Publication number
CN104779381A
CN104779381A CN201510009051.5A CN201510009051A CN104779381A CN 104779381 A CN104779381 A CN 104779381A CN 201510009051 A CN201510009051 A CN 201510009051A CN 104779381 A CN104779381 A CN 104779381A
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China
Prior art keywords
secondary cell
compound
group
lithium
current potential
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三田洋树
小谷徹
洼田忠彦
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Murata Northeast China
Murata Manufacturing Co Ltd
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Sony Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L58/00—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles
    • B60L58/10—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0431—Cells with wound or folded electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/425—Structural combination with electronic components, e.g. electronic circuits integrated to the outside of the casing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Power Engineering (AREA)
  • Transportation (AREA)
  • Mechanical Engineering (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Microelectronics & Electronic Packaging (AREA)

Abstract

A secondary battery including a cathode, an anode, and a non-aqueous electrolytic solution, in which the cathode includes an electrode compound which absorbs and releases an electrode reactant at a potential of 4.5 V or higher (potential versus lithium), and the non-aqueous electrolytic solution includes a silyl compound where one or two or more silicon-oxygen-containing groups (SiR3-O-: the three R's are respectively any one of a monovalent hydrocarbon group and a halogenated group thereof) are bonded with an atom other than silicon.

Description

Secondary cell, battery pack, motor vehicle, power storage system and electric tool
The cross reference of related application
This application requires that the Japan of submitting on January 15th, 2014 is in the rights and interests of first patent application JP2014-004811, and its full content is incorporated to herein by reference.
Technical field
This technology relate to a kind of be provided with positive pole, negative pole and nonaqueous electrolytic solution secondary cell and the battery pack using this secondary cell, motor vehicle, power storage system, electric tool and electronic equipment.
Background technology
In recent years, widely use the various electronic equipments such as such as mobile phone and personal digital assistant (PDA), be strongly required to reduce further the size of these electronic equipments and weight and realize its long-life.Therefore, as power supply, developed the battery that can obtain high-energy-density, particularly small-sized and lightweight secondary cell.
Recently, considered such secondary cell to be applied to various application, and be not limited to above-mentioned electronic installation.The example of various application comprises connecting the battery pack, motor vehicle (such as electric automobile), electric power storage system (such as household power server) and the electric tool (such as electric drill) that to be arranged on removably on electronic equipment etc.
Propose and utilized various charge-discharge principle to obtain the secondary cell of battery capacity.But, use the absorption of electrode reaction thing and the secondary cell of release to attract attention.Reason to obtain the energy density higher than excide battery, nickel-cadmium cell etc.
Secondary cell is provided with positive pole, negative pole and nonaqueous electrolytic solution.Positive pole comprise relate to discharge and recharge reaction positive active material and negative pole comprise relate to discharge and recharge reaction negative electrode active material.Nonaqueous electrolytic solution comprises nonaqueous solvents and electrolytic salt.Because the characteristic of configuration to battery of secondary cell has a significant impact, the configuration of secondary cell therefore to be thought over.
Particularly, in order to improve output characteristic etc., cobalt acid lithium (LiCoO 2) etc. be used as positive active material and three (trimethylsilyl) phosphite etc. is used as the additive of nonaqueous electrolytic solution (such as, see Japanese Unexamined Patent Application open 2001-283908, No.2007-123097, No.2008-130544 and No.2013-229341).
Summary of the invention
Constantly achieve the high-performance of electronic equipment etc. and multi-functional.Therefore, the frequency of utilization of electronic equipment etc. increases, and therefore, secondary cell is frequent discharge and recharge often.Therefore, there is the space of improving the battery behavior of secondary cell.
Expect to provide a kind of secondary cell, battery pack, motor vehicle, power storage system, electric tool and the electronic equipment that can obtain excellent specific property.
The secondary cell of the execution mode of this technology comprises positive pole, negative pole and nonaqueous electrolytic solution.Described positive pole is included in the electrode compound that more than 4.5V current potential (current potential to lithium) absorbs and discharges electrode reaction thing.Nonaqueous electrolytic solution comprises silyl compound, and wherein one or two is above containing siloxy (SiR 3-O-: three R are any one in univalence hydrocarbyl and its halogeno-group respectively) with silicon beyond atomistic binding.
The battery pack of another execution mode of this technology, motor vehicle, power storage system, electric tool or electronic equipment comprise secondary cell, and the configuration of this secondary cell is identical with the secondary cell of this above-mentioned technology.
Here, the type of silyl compound is not particularly limited, as long as silyl compound comprises one or more compound containing the structure of the atomistic binding beyond siloxy and silicon." univalence hydrocarbyl " is the general terms of the monoradical formed by carbon (C) and hydrogen (H).Univalence hydrocarbyl can be linear form can be maybe the branched form with one or more side chain.In addition, univalence hydrocarbyl can be the saturated hydrocarbyl not comprising carbon carbon multikey can be maybe the unsaturated alkyl comprising one or more carbon carbon multikey.Carbon carbon multikey is the one or both in carbon-carbon double bond (>C=C<) and carbon carbon triple bond (-C ≡ C-)." halogeno-group " is the group that one or more alkyl (-H) halogen radical in above-mentioned univalence hydrocarbyl replaces.The type of halogen radical is not particularly limited, as long as described type is any one type in the group formed by halogens or two or more type.
According to the secondary cell of the execution mode of this technology, because positive pole comprises above-mentioned electrode compound and nonaqueous electrolytic solution comprises above-mentioned silyl compound, excellent battery behavior therefore can be obtained.In addition, identical effect can also be obtained in the battery pack of the execution mode of this technology, motor vehicle, power storage system, electric tool or electronic equipment.
Accompanying drawing explanation
Fig. 1 shows the sectional view of the configuration of the secondary cell (column type) of the execution mode of this technology.
Fig. 2 amplifies and shows the sectional view of a part for the rolled electrode bodies shown in Fig. 1.
Fig. 3 show according to this implementer formula another in the perspective view of configuration of secondary cell (laminated membrane type).
Fig. 4 is the sectional view intercepted along the IV-IV line of the rolled electrode bodies shown in Fig. 3.
Fig. 5 shows the perspective view of the configuration of the application examples (battery pack: single battery) of secondary cell.
Fig. 6 shows the block diagram of the configuration of the battery pack shown in Fig. 5.
Fig. 7 shows the block diagram of the configuration of the application examples (battery pack: assembled battery) of secondary cell.
Fig. 8 shows the block diagram of the configuration of the application examples (motor vehicle) of secondary cell.
Fig. 9 shows the block diagram of the configuration of the application examples (power storage system) of secondary cell.
Figure 10 shows the block diagram of the configuration of the application examples (electric tool) of secondary cell.
Embodiment
Provide the detailed description of this implementer formula below with reference to accompanying drawings.Here, the order of description is as described below.
1, secondary cell
1-1, column type
1-2, laminated membrane type
2, the application of secondary cell
2-1, battery pack (single battery)
2-2, battery pack (assembled battery)
2-3, motor vehicle
2-4, power storage system
2-5, electric tool
1, secondary cell
First, the description of the secondary cell of this implementer formula will be provided.
1-1, column type
Each of Fig. 1 and Fig. 2 shows the cross-sectional configurations of the secondary cell of this implementer formula and the rolled electrode bodies 20 shown in Fig. 1 amplifies in fig. 2.
The configured in one piece of secondary cell
Secondary cell described herein is such as the lithium rechargeable battery that can obtain capacity owing to absorbing and discharge lithium (it is electrode reaction thing) in negative pole 22.
Secondary cell is such as so-called cylinder type secondary battery and rolled electrode bodies 20 and a pair insulation board 12 and 13 are stored in the inside of battery case 11 of the cylinder form with hollow substantially.Rolled electrode bodies 20 is such as wound around after positive pole 21 and negative pole 22 are via barrier film 23 lamination.
Battery case 11 has an end-enclosed and the hollow structure opened of another end, such as, by any one in iron (Fe), aluminium (Al), its alloy etc. or two or morely to be formed.Nickel (Ni) etc. can be plated on the surface of battery case 11.Rolled electrode bodies 20 between this is to insulation board 12 and 13 and this insulation board is arranged as relative to winding peripheral surface orthogonal extension.
Because battery cover 14, relief valve mechanism 15 and resistance thermometer clement (PTC element) 16 to be clogged via packing ring 17 and battery case 11 is sealed in the open end of battery case 11.Battery cover 14 is such as because the material that battery case 11 is identical is formed.Relief valve mechanism 15 and resistance thermometer clement 16 are arranged on inside battery cover 14 and relief valve mechanism 15 is electrically connected via resistance thermometer clement 16 and battery cover 14.In relief valve mechanism 15, when internal pressure due to internal short-circuit, from outside heat etc. and when reaching more than certain level, disk 15A is reversed.Due to this point, and cut off the electrical connection between battery cover 14 and rolled electrode bodies 20.The abnormal heat generation caused to prevent big current, the resistance of resistance thermometer clement 16 increases according to temperature and increases.Packing ring 17 is such as formed by insulating material and pitch etc. can be coated on the surface of packing ring 17.
Such as, centrepin 24 is inserted in the center of rolled electrode bodies 20.But centrepin 24 not necessarily must be inserted in the center of rolled electrode bodies 20.Such as, the positive wire 25 formed by electric conducting material (such as aluminium) is connected with positive pole 21, and such as, the negative wire 26 formed by electric conducting material (such as nickel) is connected with negative pole 22.Positive wire 25 to be welded in relief valve mechanism 15 and to be electrically connected with battery cover 14.Negative wire 26 to be welded on battery case 11 and to be electrically connected with battery case 11.
Positive pole
Positive pole 21 has positive electrode active material layer 21B on a surface or two surfaces of positive electrode collector 21A.Positive electrode collector 21A is such as formed by electric conducting material such as aluminium, nickel or stainless steel.
Positive electrode active material layer 21B comprises positive active material.But, positive electrode active material layer 21B can also comprise in other materials such as positive electrode binder and positive conductive agent any one or two or more.
Positive active material comprise can absorb and discharge in the positive electrode of electrode reaction thing any one or two or more.Particularly, the current potential (current potential to lithium) that positive electrode is included in more than 4.5V absorb and release electrode reaction thing electrode compound (hereinafter referred to as " high-potential material ") in any one or two or more.
Positive electrode comprises high-potential material.Reason obtains high battery capacity owing to increasing from the amount of the electrode reaction thing of positive electrode release between charge period.Here, " electrode reaction thing " is the material that relates in electrode reaction and is such as due to the absorption of lithium and release and the lithium obtained in the lithium rechargeable battery of its capacity.
The type of high-potential material is not particularly limited, as long as this material can absorb and release electrode reaction thing at the current potential of more than 4.5V (current potential to lithium).High-potential material can absorb and release electrode reaction thing by the current potential within the scope of this.Even if reason also can suppress the reduction of battery capacity when recharge and electric discharge, because inhibit the decomposition reaction in the electrolyte caused by the reactivity of positive pole 21 (positive active material).
The type of high-potential material is such as can absorb and discharge lithium as any one in the material of electrode reaction thing or two or more.More specifically, high-potential material is such as comprise one or more oxides as component in lithium and other elements.
Wherein, high-potential material can be preferably in the compound (lithium-containing compound) represented by formula (1) to formula (3) respectively any one or two or more.Reason can obtain (synthesis) high-potential material easily and obtain ability density.
Li 1+a(Mn bCo cNi 1-b-c) 1-aM1 dO 2-e(1)
(M1 is at least one (not comprising manganese (Mn), cobalt (Co) and nickel (Ni)) in the element of the 2nd race to the 15th race belonging to long period type periodic table, a to e meets 0<a<0.25,0.3≤b<0.7,0≤c<1-b, 0≤d≤1 and 0≤e≤1.)
Li fNi 1-g-hMn gM2 hO 2-iX j(2)
(M2 is at least one (not comprising nickel and manganese) in the element of the 2nd race to the 15th race belonging to long period type periodic table, X is at least one (not comprising oxygen (O)) belonged in the 16th race of long period type periodic table and the element of the 17th race, and f to j meets 0≤f≤1.5,0≤g≤1,0≤h≤1 ,-0.1≤i≤0.2 and 0≤j≤0.2.)
LiM3 kMn 2-kO 4(3)
(M3 is at least one (not comprising manganese) in the element of the 2nd race to the 15th race belonging to long period type periodic table, and k meets 0<k≤1.)
Lithium-containing compound (hereinafter referred to as " the first lithium-containing compound ") shown in formula (1) has the lithium composite xoide of rocksalt-type crystal structure.
First lithium-containing compound is the so-called compound being rich in lithium, as passable as apparent from the scope can getting a value.First lithium-containing compound also comprises manganese and nickel as component except lithium, as can as apparent from the span of b and c value.Here, the first lithium-containing compound can comprise or not comprise each in cobalt and another element (M1) as component.
The type of M1 is not particularly limited, if described type be in the element of the 2nd race to the 15th race belonging to long period type periodic table any one or two or more.But, from the candidate of M1, get rid of manganese, cobalt and nickel.
The instantiation of M1 be in nickel, cobalt, magnesium (Mg), aluminium, boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), zirconium (Zr), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), tungsten (W), silicon (Si) and barium (Ba) any one or two or more.
Wherein, M1 can be preferably in nickel, cobalt, chromium, iron and copper any one or two or more.Reason to obtain higher energy density.
The instantiation of the first lithium-containing compound is Li 1.2(Mn 0.5ni 0.5) 0.8o 2, Li 1.15(Mn 0.65ni 0.22co 0.13) 0.85o 2, Li 1.13(Mn 0.6ni 0.2co 0.2) 0.87al 0.01o 2deng.But the instantiation of the first lithium-containing compound can be compound in addition to the above-mentioned compounds.
Lithium-containing compound (hereinafter referred to as " the second lithium-containing compound ") shown in formula (2) is the lithium composite xoide in the mode identical with above-mentioned first lithium-containing compound with rocksalt-type crystal structure.
Second lithium-containing compound is the compound being rich in lithium, as can as apparent from the span of f value.Second lithium-containing compound can comprise or not comprise nickel, manganese and another element (M2) each as component, as can as apparent from the span of g and h value.In addition, the second lithium-containing compound can comprise or not comprise another element (X) as component, as can as apparent from the span of j value.
The type of M2 is not particularly limited, if described type be in the element of the 2nd race to the 15th race belonging to long period type periodic table any one or two or more.But, from the candidate of M2, get rid of nickel and manganese.
The instantiation of M2 be in cobalt, magnesium, aluminium, boron, titanium, vanadium, chromium, iron, copper, zinc, zirconium, molybdenum, tin, calcium, strontium, tungsten, silicon and barium any one or two or more.
Wherein, M2 can be preferably in cobalt, chromium, iron and copper any one or two or more.Reason to obtain higher energy density.
The type of X is not particularly limited, if described type be belong in the 16th race of long period type periodic table and the element of the 17th race any one or two or more.But, from the candidate of X, get rid of oxygen.
The instantiation of X be in fluorine (F), chlorine (Cl), bromine (Br) and iodine (I) any one or two or more.
Wherein, X can be preferably in halogens any one or two or more and X is more preferably fluorine.Reason to obtain higher energy density.
Here, f is not particularly limited, as long as meet 0≤f≤1.5.But, especially, preferably meet 0<f≤1.5.Reason obtains higher energy density because the second lithium-containing compound is rich in lithium.
Or h is not particularly limited, as long as meet 0≤h≤1.But, especially, preferably meet 0≤h<1.Reason be due to the second lithium-containing compound comprise in nickel and manganese one or both obtain higher energy density as component.
The instantiation of the second lithium-containing compound is LiCoO 2, Li (Ni 0.5co 0.2mn 0.3) O 2, Li (Ni 0.33co 0.33mn 0.33) O 2deng.But the instantiation of the second lithium-containing compound can be compound in addition to the above-mentioned compounds.
Lithium-containing compound (hereinafter referred to as " the 3rd lithium-containing compound ") shown in formula (3) is the lithium composite xoide with spinel type crystal structure.
3rd lithium-containing compound also comprises another element (M3) as component except manganese, as can as apparent from the span of k value.
The type of M3 is not particularly limited, if described type be in the element of the 2nd race to the 15th race belonging to long period type periodic table any one or two or more.But, from the candidate of M3, get rid of manganese.
The instantiation of M3 be in nickel, cobalt, magnesium, aluminium, boron, titanium, vanadium, chromium, iron, copper, zinc, zirconium, molybdenum, tin, calcium, strontium, tungsten, silicon and barium any one or two or more.
Wherein, M3 can be preferably in nickel, cobalt, chromium, iron and copper any one or two or more.Reason to obtain higher energy density.
The instantiation of the 3rd lithium-containing compound is Li (Mn 1.5ni 0.5) O 4, LiCoMnO 4deng.But the instantiation of the 3rd lithium-containing compound can be compound in addition to the above-mentioned compounds.
First lithium-containing compound, the second lithium-containing compound and the 3rd lithium-containing compound are hereafter being referred to as " specific lithium-containing compound ".
In order to confirm, in the de-scription, the execution mode that positive electrode comprises specific lithium-containing compound is not particularly limited.
Particularly, if positive electrode comprise in the first lithium-containing compound, the second lithium-containing compound and the 3rd lithium-containing compound any one or two or more just enough.That is, positive electrode can only include in the first lithium-containing compound, the second lithium-containing compound and the 3rd lithium-containing compound any one, two kinds in combination in any can be comprised, maybe can comprise all these three kinds.
In addition, positive electrode can comprise in the first lithium-containing compound any one or two or more.That is, any one compound that positive electrode can only include in a series of compounds corresponding with the first lithium-containing compound maybe can comprise the two or more of combination in any.This is applicable to each in the second lithium-containing compound and the 3rd lithium-containing compound in an identical manner.
Here, positive electrode may further include in other materials any one or two or more, as long as positive electrode comprises above-mentioned specific lithium-containing compound.
Other materials is such as other lithium-containing compounds such as lithium-transition metal composite oxides and lithium transition metal phosphates compound.Lithium-transition metal composite oxide comprises lithium and the oxide of one or more transition metals as component.But, from lithium-transition metal composite oxide, get rid of the compound corresponding with specific lithium-containing compound.Lithium transition metal phosphates compound comprises lithium and the phosphate compounds of one or more transition metals as component.Wherein, transition metal can be preferably in nickel, cobalt, manganese, iron etc. any one or two or more.Reason to obtain higher voltage.Chemical formula such as uses Li xm11O 2or Li ym12PO 4represent.M11 and M12 in chemical formula is one or more in transition metal.The value of x and y is different according to charging and discharging state, but is generally 0.05≤x≤1.10 and 0.05≤y≤1.10.
Except having the LiNiO of rocksalt-type crystal structure 2deng outside, the instantiation of lithium-transition metal composite oxide has the LiMn of spinel type crystal structure in addition 2o 4deng.The instantiation of lithium transition metal phosphates compound is the LiFePO with olivine-type crystal structure 4, LiFe 1-umn upO 4(u<1) etc.
In addition, other materials be such as in oxide, disulphide, chalcogen compound (chalcogenides) and conducting polymer any one or two or more.Oxide is such as titanium oxide, vanadium oxide, manganese dioxide etc.Disulphide is such as titanium disulfide, molybdenum bisuphide etc.Chalcogen compound is such as selenizing niobium etc.Conducting polymer is such as sulphur, polyaniline, polythiophene etc.
Positive electrode binder such as comprise in synthetic rubber, polymeric material etc. any one or two or more.Synthetic rubber is such as butadiene-styrene system rubber, fluorine system rubber, Ethylene-Propylene-Diene etc.Polymeric material is such as polyvinylidene fluoride, polyimides etc.The crystal structure being used as the polyvinylidene fluoride of polymeric material is not particularly limited.
Positive conductive agent such as comprise in material with carbon element etc. any one or two or more.Material with carbon element is such as graphite, carbon black, acetylene black, Ketjen black etc.Here, positive conductive agent can be metal material, conducting polymer etc., as long as described material has conductivity.
Negative pole
Negative pole 22 has negative electrode active material layer 22B on a surface or two surfaces of negative electrode collector 22A.
Negative electrode collector 22A is such as formed by electric conducting material such as copper, nickel or stainless steel.The surface of negative electrode collector 22A is preferably roughened.Reason is that the adhesiveness of negative electrode active material layer 22B anticathode collector body 22A improves due to so-called anchoring effect.In this case, the surface of negative electrode collector 22A can at least be roughened in the region relative with negative electrode active material layer 22B.The method of roughening is such as the method using electrolytic treatments to form molecule.Electrolytic treatments is following method: arrange concavo-convex on the surface of negative electrode collector 22A by using electrolytic method to form molecule in a cell on the surface of negative electrode collector 22A.The Copper Foil of electrolytic method manufacture is used to be commonly referred to as electrolytic copper foil.
Negative electrode active material layer 22B comprise can absorb and discharge in the negative material of electrode reaction thing any one or two or more as negative electrode active material.But, negative electrode active material layer 22B can comprise further in other materials such as negative electrode binder and cathode conductive agent any one or two or more.Here, about the details of negative electrode binder and cathode conductive agent with identical with the details of positive conductive agent about positive electrode binder.
But in order to prevent electrode reaction thing to be deposited to unintentionally between charge period on negative pole 22, the chargeable capacity of negative material is preferably greater than the discharge capacity of positive pole 21.That is, the electrochemical equivalent that can absorb and discharge the negative material of electrode reaction thing is preferably greater than the electrochemical equivalent of positive pole 21.Here, when electrode reaction thing is lithium, the electrode reaction thing be deposited on negative pole 22 is such as lithium metal.
Negative material be such as in material with carbon element any one or two or more.Reason be due to absorb and release electrode reaction thing time crystal structure change very little and stably can obtain high-energy-density.In addition, reason is that the conductivity of negative electrode active material layer 22B improves because material with carbon element also has the function of cathode conductive agent.
Material with carbon element is such as graphitized carbon, difficult graphitized carbon, graphite etc.But the spacing on (002) in difficult graphitized carbon surface is preferably more than 0.37nm and the spacing on (002) surface in graphite is preferably below 0.34nm.More specifically, material with carbon element is such as RESEARCH OF PYROCARBON, coke, vitreous carbon fibers, organic high molecular compound fired body, active carbon, carbon black etc.These coke comprise pitch coke, needle coke, petroleum coke etc.Organic high molecular compound fired body is formed by the macromolecular compound such as phenol resin or furane resins firing (carbonization) at moderate temperatures.In addition, material with carbon element can be that at the temperature of about less than 1000 DEG C, perform heat treated low-crystallinity carbon can be maybe amorphous carbon.Here, the shape of material with carbon element can be any one in fiber shape, ball shape, grain shape or scale shape.
In addition, negative material is such as any one or the two or more material as component (metal based material) that comprise in metallic element and semimetallic elements.Reason to obtain high-energy-density.
Metal based material can be any one in simple substance, alloy or compound, and can be wherein two or more, can be maybe the material at least partly with wherein one or more phase.But, except the material formed by two or more metallic element, in alloy, also include one or more the material in one or more and the semimetallic elements comprised in metallic element.In addition, alloy can comprise nonmetalloid.The form of metal based material is such as solid solution, eutectic crystal (eutectic mixture), intermetallic compound, have wherein two or more coexisting substances etc.
Above-mentioned metallic element and semimetallic elements be such as can be formed in the metallic element of alloy and electrode reaction thing and semimetallic elements any one or two or more.Particularly, such as, metallic element and semimetallic elements are magnesium, boron, aluminium, gallium, indium (In), silicon, germanium (Ge), tin, lead (Pb), bismuth (Bi), cadmium (Cd), silver (Ag), zinc, zirconium, hafnium (Hf), yttrium (Y), palladium (Pd), platinum (Pt) etc.
Wherein, the one or both in silicon and tin is preferred.Reason can obtain too high energy density due to absorption and the ability excellence discharging electrode reaction thing.
Comprising the one or both in silicon and tin as the material of component can be any one in the simple substance of silicon, alloy or compound, can be any one in the simple substance of tin, alloy or compound, can be wherein two or more, can be maybe the material of one or more the phase had at least partly wherein.Here, simple substance only has the implication (it can comprise very small amount of impurity) of simple substance and the implication of not necessarily 100% purity in general sense.
The alloy of silicon such as comprise in tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony, chromium etc. any one or two or more as the component outside silica removal.The compound of silicon such as comprise in carbon, oxygen etc. any one or two or more as the component outside silica removal.Here, the compound of silicon such as can comprise in the series of elements that the alloy about silicon describes any one or two or more as the component outside silica removal.
The instantiation of the alloy of silicon and the compound of silicon is SiB 4, SiB 6, Mg 2si, Ni 2si, TiSi 2, MoSi 2, CoSi 2, NiSi 2, CaSi 2, CrSi 2, Cu 5si, FeSi 2, MnSi 2, NbSi 2, TaSi 2, VSi 2, WSi 2, ZnSi 2, SiC, Si 3n 4, Si 2n 2o, SiO v(0<v≤2), LiSiO etc.Here, SiO vin v can be 0.2<v<1.4.
The alloy of tin such as comprise in silicon, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony, chromium etc. any one or two or more as the component outside detin.The compound of tin such as comprise in carbon, oxygen etc. any one or two or more as the component outside detin.Here, the compound of tin such as can comprise in the series of elements that the alloy about tin describes any one or two or more as the component outside detin.
The instantiation of the alloy of tin and the compound of tin is SnO w(0<w≤2), SnSiO 3, LiSnO, Mg 2sn etc.
Particularly, comprise tin as the material preference of component also comprise outside detin (the first component) in this way second and the 3rd component as the material (material containing Sn) of component.Second component such as comprise in cobalt, iron, magnesium, titanium, vanadium, chromium, manganese, nickel, copper, zinc, gallium, zirconium, niobium, molybdenum, silver, indium, caesium (Ce), hafnium (HF), tantalum, tungsten, bismuth, silicon etc. any one or two or more.3rd component such as comprise in boron, carbon, aluminium, phosphorus (P) etc. any one or two or more.Reason can obtain high battery capacity when the material containing Sn comprises second and the 3rd component, excellent cycle characteristics etc.
Wherein, the material containing Sn preferably includes tin, cobalt and the carbon material (material containing SnCoC) as component.Containing in the material of SnCoC, such as, the content of carbon is 9.9 quality % to 29.7 quality % and the ratio (Co/ (Sn+Co)) containing lithium of tin and cobalt is 20 quality % to 70 quality %.Reason to obtain high-energy-density.
Material containing SnCoC has the phase that comprises tin, cobalt and carbon and this is preferably low-crystalline or amorphous mutually.Because this is the reacting phase that can react with electrode reaction thing mutually, therefore obtain excellent characteristic due to reacting phase.When CuK alpha ray is used as specific X ray and insertion and pull-out speed are set to 1 °/min, the half breadth (angle of diffraction 2 θ) of the diffraction maximum obtained by the X-ray diffraction of reacting phase is preferably more than 1 °.Reason is that electrode reaction thing absorbs more smoothly and discharges and reduces with the reactivity of electrolyte.Here, also there is such situation, the material wherein containing SnCoC comprises and also comprise each simple substance of component or the phase of a part except low-crystalline or amorphous phase.
Can by with compare the diffraction maximum that X-ray diffractogram determines to be obtained by X-ray diffraction easily before and after electrode reaction thing electrochemical reaction and whether correspond to the reacting phase that can react with electrode reaction thing.Such as, when diffraction maximum position with electrode reaction thing electrochemical reaction before and after change time, diffraction maximum corresponds to the reacting phase that can react with electrode reaction thing.In this case, such as, the diffraction maximum of low-crystalline or amorphous reacting phase, i.e. 2 θ, see between 20 ° and 50 °.This reacting phase such as comprise above-mentioned component each and think mainly due to there is carbon but low-crystalline or unbodied.
In the material containing SnCoC, the preferred at least partially and metallic element in carbon (as being component) or semimetallic elements (as another component) bonding.Reason suppresses cohesion or the crystallizations such as tin.X-ray photoelectron spectroscopy (XPS) such as can be used to confirm the bond styles of element.In the device of commercialization, such as, Al-K alpha ray, Mg-K alpha ray etc. can be used as grenz ray.In carbon at least partially with the bonding such as metallic element, semimetallic elements, the peak of the composite wave of the 1s track (C1s) of carbon appears in the region lower than 284.5eV.Here, carrying out energy calibration makes the peak of the 4f track (Au4f) of gold atom obtain at 84.0eV place.Now, in general, because surface contamination carbon is present on material surface, therefore the peak of the C1s of surface contamination carbon is set to 284.8eV and this peak is set to energy reference.In XPS measuring, the waveform at the peak of C1s is to comprise the peak of surface contamination carbon and to obtain containing the form at the peak of the carbon in the material of SnCoC.Due to this point, such as, the peak of both uses business software to be separated by analyzing.In the process of analysis waveform, the position of the main peak being present in minimum binding energy side is set to energy reference (284.8eV).
Material containing SnCoC is not limited to the material (SnCoC) that component is only tin, cobalt and carbon.Containing SnCoC material except tin, cobalt and carbon as can further include except component in such as silicon, iron, nickel, chromium, indium, niobium, germanium, titanium, molybdenum, aluminium, phosphorus, gallium, bismuth etc. any one or two or more.
Except containing except the material of SnCoC, comprising tin, cobalt, iron and carbon as the material (material containing SnCoFeC) of component is preferred equally.Composition containing the material of SnCoFeC is arbitrary.Such as, when the content of iron is set to lower, the content of carbon is 9.9 quality % to 29.7 quality %, and the content of iron is 0.3 quality % to 5.9 quality %, and the ratio (Co/ (Sn+Co)) of the content of tin and cobalt is 30 quality % to 70 quality %.In addition, when the content of iron is set to larger, the content of carbon is 11.9 quality % to 29.7 quality %, the ratio ((Co+Fe)/(Sn+Co+Fe)) of the content of tin, cobalt and iron is 26.4 quality % to 48.5 quality %, and the ratio of the content of cobalt and iron (Co/ (Co+Fe)) is 9.9 quality % to 79.5 quality %.Reason can obtain high-energy-density in this combination range.Here, the physical property (half breadth etc.) containing the material of SnCoFeC is identical with the physical property of the above-mentioned material containing SnCoC.
In addition, negative material can be such as in metal oxide, macromolecular compound etc. any one or two or more.Metal oxide is such as iron oxide, ruthenium-oxide, molybdenum oxide etc.Macromolecular compound is such as polyacetylene, polyaniline, polypyrrole etc.
Wherein, for following reason, negative material preferably includes material with carbon element and metal based material.
For metal based material, especially, for comprising the material of the one or both in silicon and tin as component, there is the advantage that theoretical capacity is higher, but worry material easily strong expandable and contraction when electrode reaction.On the other hand, for material with carbon element, worry that theoretical capacity is lower, but there is this material is not easy enlargement and contraction advantage when electrode reaction.Therefore, by using material with carbon element and metal based material, suppress enlargement and contraction during electrode reaction to obtain higher theoretical capacity (in other words, battery capacity) simultaneously.
Negative electrode active material layer 22B is formed by any one in such as cladding process, vapor phase method, liquid phase method, thermal spray methods, firing process (sintering process) etc. or two or more methods.Cladding process is such as following method: mixed with negative electrode binder etc. by the negative electrode active material of particle (powder) form, mixture is dispersed in ratio of solvent as in organic solvent, then utilize gains to apply negative electrode collector 22A.Vapor phase method is such as physical deposition methods, chemical deposition etc.More specifically, such as, vapor phase method is vaccum gas phase sedimentation method, sputtering method, ion plating, laser ablation method, thermal chemical vapor deposition, chemical vapour deposition (CVD) (CVD) method, plasma chemical vapor deposition etc.Liquid phase method is such as electrolytic plating method, plated by electroless plating method etc.Thermal spray methods is the method sprayed to by the negative electrode active material under molten condition or semi-molten state on negative electrode collector 22A.Firing process is such as that the mixture disperseed in solvent uses cladding process to be coated on negative electrode collector 22A, then at the temperature higher than the fusing point of negative electrode binder etc., performs heat-treating methods to product.Air firing process, reaction firing process, hot pressing firing process etc. such as can be used as firing process.
In the secondary battery, as mentioned above, in order to prevent electrode reaction thing between charge period to be deposited to unintentionally on negative pole 22, the electrochemical equivalent that can absorb and discharge the negative material of electrode reaction thing is greater than the electrochemical equivalent of positive pole.In addition, when being full of electricity open circuit voltage (, cell voltage) for more than 4.25V time, even if owing to using identical positive active material, the burst size of the electrode reaction thing of per unit mass is larger compared with the situation of 4.20V, and therefore the amount of positive active material and negative electrode active material adjusts according to this situation.Due to this point, and obtain high-energy-density.
Barrier film
Positive pole 21 and negative pole 22 separate by barrier film 23, and while preventing the short circuit current caused by the contact of two electrodes, lithium ion are passed through.Barrier film 23 is such as perforated membrane such as synthetic resin or pottery, and can be the wherein lamination laminated film of two or more perforated membrane.Synthetic resin is such as polytetrafluoroethylene, polypropylene and polyethylene etc.
Especially, barrier film 23 can comprise such as above-mentioned perforated membrane (substrate material layer) and be arranged on the macromolecular compound layer on a surface of substrate material layer or two surfaces.Reason improves the adhesion characteristics of barrier film 23 relative to positive pole 21 and negative pole 22, inhibits the distortion of rolled electrode bodies 20.Due to this point, owing to inhibit the decomposition reaction of electrolyte, thus inhibit the leak of liquid of the electrolyte of dipping substrate material layer, even if repeat discharge and recharge, resistance also not easily increases, and inhibits cell expansion.
Macromolecular compound layer comprise such as macromolecular material as polyvinylidene fluoride.Reason is that this macromolecular material has excellent physical strength and is electrochemical stability.But macromolecular material can be the material except polyvinylidene fluoride.When forming macromolecular compound layer, after having prepared and being wherein dissolved with the solution of macromolecular material, utilizing solution coat base material, and subsequently drying having been carried out to gains.Here, substrate material layer can be soaked in the solution, carry out drying subsequently.
Electrolyte
Nonaqueous electrolytic solution (hereinafter referred to as " electrolyte ") is immersed in rolled electrode bodies 20, and this electrolyte is the electrolyte of liquid form.
Electrolyte comprise in silyl compound any one or two or more.Silyl compound is that one or more contain siloxy (SiR 3-O-: three R are any one in univalence hydrocarbyl and its halogeno-group respectively) with silicon beyond atom (hereinafter referred to as " non-silicon atoms ") bonding.
The type of silyl compound is not particularly limited, as long as compound comprises the structure that one or more contain siloxy and non-silicon atoms bonding.Quantity containing siloxy is determined according to the type (quantity of atomic bond) of non-silicon atoms.Three R can be identical types can be maybe dissimilar.Certainly, can in three R only two be identical type.
The type of non-silicon atoms is not particularly limited, as long as atom is the atom except silicon atom.Wherein, non-silicon atoms is preferably any one atom in aluminium, boron, phosphorus, sulphur, carbon and hydrogen.Reason can synthesize silyl compound easily.
" univalence hydrocarbyl " is the general terms of the monoradical formed by carbon and hydrogen.Univalence hydrocarbyl can be linear form can be maybe the branched form with one or more side chain.In addition, univalence hydrocarbyl can be the saturated hydrocarbyl not comprising carbon carbon multikey can be maybe the unsaturated alkyl comprising one or more carbon carbon multikey.Carbon carbon multikey is the one or both in carbon-carbon double bond (>C=C<) and carbon carbon triple bond (-C ≡ C-).
Particularly, univalence hydrocarbyl is such as any one in alkyl, alkenyl, alkynyl, cycloalkyl, aryl and two or more monoradical be bonded to wherein.
The carbon atom of univalence hydrocarbyl is not particularly limited.Wherein, the carbon number amount of alkyl is preferably 1 to 8 and the carbon number amount of each of alkenyl and alkynyl is preferably 2 to 8.The carbon number amount of cycloalkyl is preferably 3 to 18, and the carbon number amount of aryl is preferably 6 to 18.Reason is the dissolubility, intersolubility etc. that ensure that silyl compound.
The instantiation of alkyl is methyl (-CH 3), ethyl (-C 2h 5), propyl group (-C 3h 7), normal-butyl (-C 4h 8), the tert-butyl group (-C (-CH 3) 2-CH 3) etc.The instantiation of alkenyl is vinyl (-CH=CH 2), pi-allyl (-CH 2-CH=CH 2) etc.The instantiation of alkynyl is acetenyl (-C ≡ CH) etc.
The instantiation of cycloalkyl is cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, ring octyl group etc.The instantiation of aryl is phenyl, naphthyl etc.
" the two or more monoradical be bonded to " is the group (hereinafter referred to as " unit price binding groups ") that two or more bondings in above-mentioned univalence hydrocarbyl become unit price on the whole.Unit price binding groups is such as the group etc. of the group of the group of the group of the group of alkyl and alkenyl bonding, alkyl and alkynyl bonding, alkenyl and alkynyl bonding, alkyl and aryl bonding, alkyl and cycloalkyl bonding.
" halogeno-group " is the group that one or more hydrogen base (-H) halogen radical in above-mentioned univalence hydrocarbyl replaces.The type of " halogen radical " is not particularly limited, but, such as, described type be in fluorine-based (-F), chloro (-Cl), bromo (-Br), iodo (-I) etc. any one or two or more.
Here, R can be the group except above-mentioned group.Other groups are such as unit price oxygen-containing hydrocarbon base, its halogeno-group etc." unit price oxygen-containing hydrocarbon base " is by the general terms also comprising the monoradical that oxygen is formed outside de-carbon and hydrogen.Unit price oxygen-containing hydrocarbon base can be linear form can be maybe the branched form with one or more side chain.In addition, unit price oxygen-containing hydrocarbon base can comprise or not comprise one or more carbon carbon multikey.
Particularly, unit price oxygen-containing hydrocarbon base to be such as carbon number amount be 1 to 8 alkoxyl.Reason is the dissolubility, intersolubility etc. that ensure that silyl compound.The instantiation of alkoxyl is methoxyl group (-OCH 3), ethyoxyl (-OC 2h 5) etc.
" halogeno-group " is the group that one or more hydrogen base halogen radical in above-mentioned unit price oxygen-containing hydrocarbon base replaces.The type of halogeno-group is described above.
More specifically, silyl compound comprise in the compound represented by formula (4) any one or two or more.
(SiR1 3-O-) m-Y (4)
(three R1 are univalence hydrocarbyl and any one in its halogeno-group respectively.Y comprises the group of any one atom in aluminium, boron, phosphorus, sulphur, carbon and hydrogen as composed atom.But, containing the ehter bond (-O-) in siloxy and any one atomistic binding in aluminium, boron, phosphorus, sulphur, carbon and the hydrogen in Y.M is the integer of more than 1.)
Details about R1 are identical with the above-mentioned details about R.
The type of Y is not particularly limited, as long as group comprises any one atom in aluminium, boron, phosphorus, sulphur, carbon and hydrogen as composed atom (hereinafter referred to as " ground atom ").That is, Y can only include ground atom maybe also can comprise except ground atom in other atoms any one or two or more.
As mentioned above, determine containing siloxy (SiR1 3-O-) the m value of quantity determine according to the type of Y.Such as, when the quantity of the atomic bond of Y is 1, the quantity (value of m) containing siloxy is 1.Or when the quantity of the atomic bond of Y is 3, the quantity containing siloxy is 3.
But, containing in the key between siloxy and Y, must with the ground atom bonding in Y containing the ehter bond in siloxy.This is the function (effect) in order to retain following silyl compound.
The instantiation of Y is any one group in the group represented by formula (4-21) to formula (4-31) respectively.Here, about " halogen radical ", the details of " univalence hydrocarbyl " and " halogeno-group " are described above.
(Z1 is halogen radical.Z2 and Z4 is univalence hydrocarbyl and any one in its halogeno-group.Z3 is any one group in hydrogen base and halogeno-group.Z5 is bivalent hydrocarbon radical and any one group in its halogeno-group.N is the integer of more than 1.)
The quantity of the atomic bond in Y is 1 in formula (4-26), formula (4-27), formula (4-29) and formula (4-31), be 2 in formula (4-25), formula (4-28) and formula (4-30), be 3 in formula (4-21) to formula (4-24).
" bivalent hydrocarbon radical " is the general terms of the divalent group formed by carbon and hydrogen.Bivalent hydrocarbon radical can be linear form can be maybe the branched form with one or more side chain.In addition, bivalent hydrocarbon radical can be the saturated bond not comprising carbon carbon multikey can be maybe the unsaturated alkyl comprising one or more carbon carbon multikey.
Particularly, bivalent hydrocarbon group any one group in this way in alkylidene, alkylene group, alkynylene, cycloalkylidene, arlydene and its two or more divalent groups be bonded to.
The carbon number amount of bivalent hydrocarbon radical is not particularly limited.Wherein, the carbon number amount of each of alkylidene, alkylene group and alkynylene is preferably 2 to 8.In addition, the carbon number amount of cycloalkylidene is preferably 3 to 18 and the carbon number amount of arlydene is preferably 6 to 18.Reason is the dissolubility, intersolubility etc. that ensure that silyl compound.
The instantiation of alkylidene is methylene (-CH 2-), ethylidene (-C 2h 4-), propylidene (-C 3h 6-), Aden group (-C 4h 8-) etc.The instantiation of alkylene group is ethenylidene (-CH=CH-), acrol (-CH 2-CH=CH-) etc.The instantiation of alkynylene is ethynylene (-C ≡ C-) etc.
The instantiation of cycloalkylidene is sub-cyclopropane base, sub-cyclobutane base, sub-pentamethylene base, sub-cyclohexyl, sub-cycloheptane base, sub-cyclooctane base etc.The instantiation of arlydene is phenylene, naphthylene etc.
" the two or more divalent group be combined into " is the two or more bondings in above-mentioned bivalent hydrocarbon radical is (hereinafter referred to as " bivalent bonding group ") that become divalence on the whole.Bivalent bonding group is such as the group etc. of the group of the group of the group of the group of alkylidene and alkenylene bonding, alkylidene and alkynylene bonding, alkenylene and alkynylene bonding, alkylidene and arlydene bonding, alkylidene and cycloalkylidene bonding.
" halogeno-group " is the group that one or more hydrogen base halogen radical in above-mentioned bivalent hydrocarbon radical replaces.The type of halogeno-group is described above.
The value of n is not particularly limited, as long as value is the integer of more than 1.But wherein, the integer of less than 10 is preferred.Reason is the dissolubility, intersolubility etc. that ensure that silyl compound.
The instantiation of silyl compound be in the compound represented by formula (4-1) to formula (4-17) respectively any one or two or more.But silyl compound can be the compound except following compound.
(-Me represents methyl, and-t-Bu represents the tert-butyl group.)
(-Me represents methyl and-Et represents ethyl.)
Here, electrolyte comprises silyl compound.Reason is because the chemical stability of electrolyte improves, even if when positive pole 21 is to the decomposition reaction that also can suppress electrolyte when comprising the charging/discharging of secondary cell of specific lithium-containing compound as positive active material.
Particularly, when using specific lithium-containing compound as positive active material, such as, high battery capacity is by being increased to more than 4.5V to obtain by charging voltage (upper voltage limit between charge period).On the other hand, when charging voltage increases, because the reactivity of specific lithium-containing compound is higher, therefore promote the decomposition reaction of electrolyte when repeating discharge and recharge.Due to this point, battery capacity easily reduces and easily generates gas.But when electrolyte comprises silyl compound, when charging voltage is increased to more than 4.5V, the coat film obtained from silyl compound is formed in the surface of positive pole 21 specifically.Thus, because the specific raising of the chemical stability of electrolyte, even if so when repeating discharge and recharge to the secondary cell using specific lithium compound, the decomposition reaction of electrolyte also significantly can be suppressed.Therefore, battery capacity is not easy to reduce and is not easy to generate gas.In order to confirm, in described description, owing to being difficult to when charging voltage is less than 4.5V form above-mentioned coat film, therefore substantially cannot obtain the electrolyte decomposition inhibit feature caused by silyl compound.
Here, when using the material except specific lithium-containing compound as positive active material, charging voltage inherently can not increase due to the physical property of other materials, and the decomposition reaction of the electrolyte therefore caused by high charge voltage in above-mentioned charge and discharge process is not easy to twine generation in essence.
Due to above-mentioned situation, the electrolyte decomposition inhibit feature caused by above-mentioned silyl compound shows as when positive active material specifically at the specific lithium-containing compound of use.On the other hand, the electrolyte decomposition inhibit feature caused by silyl compound can not show as when positive active material substantially at the material of use except specific lithium-containing compound.
The content of the silyl compound in electrolyte is not particularly limited.But the content of 0.01wt% to 3wt% is preferred.Reason is owing to fully having shown the decomposition reaction suppressing electrolyte due to the electrolyte decomposition inhibit feature of silyl compound further.
Here, except above-mentioned silyl compound, electrolyte can also comprise in following other materials any one or two or more.
Other materials is such as that ratio of solvent is as any one in nonaqueous solvents or two or more.
Nonaqueous solvents is such as cyclic carbonate, linear carbonate, lactone, chain carboxylate, nitrile etc.Reason is that of obtaining excellent battery capacity, cycle characteristics, storage characteristics etc.Cyclic carbonate is such as ethylene carbonate, propylene carbonate, butylene carbonate etc., and linear carbonate is such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate etc.Lactone is such as gamma-butyrolacton, gamma-valerolactone etc.Carboxylate is such as methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, acetic acid trimethyl formate, acetic acid trimethyl ethyl ester etc.Nitrile is such as acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile etc.
In addition, nonaqueous solvents can be such as 1,2-dimethoxy-ethane, oxolane, 2-methyltetrahydrofuran, oxinane, 1,3-dioxolanes, 4-methyl isophthalic acid, 3-dioxolanes, 1,3-dioxane, Isosorbide-5-Nitrae-dioxane, N, dinethylformamide, 1-METHYLPYRROLIDONE, N-methyl oxazolidinone, N, N'-methylimidazole alkane ketone, nitromethane, nitroethane, sulfolane, trimethyl phosphate and methyl-sulfoxide etc.Reason to obtain identical advantage.
Wherein, in ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate any one or two or more be preferred.Reason to obtain excellent battery capacity, cycle characteristics, storage characteristics etc.In this case, high viscosity (high-k) solvent (such as, relative dielectric constant ε >=30) as ethylene carbonate or propylene carbonate and low viscosity solvent (such as, the viscosity≤1mpas) mixture as dimethyl carbonate, methyl ethyl carbonate or diethyl carbonate be preferred.Reason to improve dissociation properties and the ionic mobility of electrolytic salt.
Especially, nonaqueous solvents can be in unsaturated cyclic carbonic ester, halocarbonate, sultone (cyclic sulfonic acid ester), acid anhydrides etc. any one or two or more.Reason is that the chemical stability of electrolyte is improved.Unsaturated cyclic carbonic ester is the cyclic carbonate with one or more unsaturated carbon bond (one or both in carbon-carbon double bond and carbon carbon triple bond), comprises such as vinylene carbonate, vinyl ethylene carbonate, carbonic acid methylene ethyl etc.Halocarbonate comprises one or more halogen as the ring-type of component or linear carbonate.Cyclic halo carbonic ester is such as 4-fluoro-1,3-dioxolan-2-one and 4,5-bis-fluoro-DOX-2-ketone etc.Chain halocarbonate is such as carbonic acid methyl fluoride methyl esters, carbonic acid two (fluorine methyl esters) and carbonic acid difluoromethyl methyl esters etc.Sultone is such as propane sultone, propene sultone etc.Acid anhydrides is such as succinic anhydride, anhydrous ethane disulfonic acid (anhydrous ethane disulfonic acid), anhydrous sulfobenzoic acid (anhydrous sulfobenzoicacid) etc.But nonaqueous solvents can be compound in addition to the above-mentioned compounds.
Electrolytic salt comprise in the salt such as such as lithium salts any one or two or more.But electrolytic salt can comprise the salt except lithium salts.Salt except lithium salts is such as the salt of the light metal except lithium.
Lithium salts is such as lithium hexafluoro phosphate (LiPF 6), LiBF4 (LiBF 4), lithium perchlorate (LiClO 4), hexafluoroarsenate lithium (LiAsF 6), tetraphenylboronic acid lithium (LiB (C 6h 5) 4), pyrovinic acid lithium (LiCH 3sO 3), trifluoromethyl sulfonic acid lithium (LiCF 3sO 3), tetrachloro-lithium aluminate (LiAlCl 4), hexafluorosilicic acid two lithium (Li 2siF 6), lithium chloride (LiCl) and lithium bromide (LiBr) etc.Reason to obtain good battery capacity, cycle characteristics, storage characteristics etc.
Wherein, LiPF 6, LiBF 4, LiClO 4and LiAsF 6in any one or two or more be preferred.Reason obtains larger effect because internal resistance reduces.But electrolytic salt can be compound in addition to the above-mentioned compounds.
The content of electrolytic salt is not particularly limited.But relative to solvent, the content of 0.3mol/kg to 3.0mol/kg is preferred.Reason to obtain high ionic conductivity.
The operation of secondary cell
Secondary cell such as operates as follows.
When charging, when lithium ion discharges from positive pole 21, lithium ion is absorbed in negative pole 22 by electrolyte.On the other hand, when discharging, when lithium ion discharges from negative pole 22, lithium ion is absorbed in positive pole 21 by electrolyte.
The manufacture method of secondary cell
Secondary cell such as manufactures according to following steps.
When manufacturing positive pole 21, first, the positive electrode active materials of any one or two or more that comprise in specific lithium-containing compound is mixed to prepare cathode mix with positive electrode binder, positive pole electric conductor etc. as required.Subsequently, cathode mix is dispersed in organic solvent etc. to obtain pasted positive mixture paste.Subsequently, utilize cathode mix slurry to be coated with two surfaces of positive electrode collector 21A, cathode mix is carried out drying to form positive electrode active material layer 21B.Subsequently, can be pressed by positive electrode active material 21B such as roll squeezers, simultaneously heating cathode active material layer 21B as required.In this case, compressing several can be repeated.
When manufacturing negative pole 22, on negative electrode collector 22A, form negative electrode active material layer 22B according to the step identical with above-mentioned positive pole 21.Particularly, after passing through that negative electrode active material and negative electrode binder, negative electrical conductors etc. are mixed to form negative electrode mix, by negative electrode mix being dispersed in the middle formation pasty state negative electrode mix slurries such as organic solvent.Subsequently, utilize negative electrode mix slurry to be coated with two surfaces of negative electrode collector 22A, negative electrode mix is carried out drying to form negative electrode active material layer 22B.Finally, be pressed by anticathode active material layer 22B such as roll squeezers.
When preparing electrolyte, after being dispersed or dissolved in solvent by electrolytic salt, any one or two or more in silyl compound can be added to solvent.
When using positive pole 21 and negative pole 22 to carry out secondary cell for assembling, by welding etc., positive wire 25 is connected to positive electrode collector 21A, and by welding etc., negative wire 26 is connected to negative electrode collector 22A.Subsequently, carry out lamination through barrier film 23 pairs of positive poles 21 and negative pole 22, and reel, form rolled electrode bodies 20 thus.Afterwards, centrepin 24 is inserted into the center of rolled electrode bodies 20.Subsequently, rolled electrode bodies 20 is clipped between a pair insulation board 12 and 13, and is contained in battery case 11.In this case, by welding etc., the end of positive wire 25 is connected to relief valve mechanism 15, and by welding etc., the end of negative wire 26 is connected to battery case 11.Subsequently, inject the electrolyte in battery case 11, and utilize electrolyte to flood barrier film 23.Finally, at the open end of battery case 11, clogged by packing ring 17 and battery cover 14, relief valve mechanism 15 and resistance thermometer clement 16 are fixed.
The operation of secondary cell and effect
According to cylinder type secondary battery, positive pole 21 comprises specific lithium-containing compound and electrolyte comprises silyl compound.In this case, as mentioned above, even if the secondary cell comprising specific lithium-containing compound when positive pole 21 discharge and recharge under comparatively high charge voltage conditions, the decomposition reaction of electrolyte also carrys out specificity by silyl compound and suppresses.Therefore, though due to when repeating discharge and recharge discharge capacity be not easy to reduce, excellent battery behavior can be obtained.
Especially, when high-potential material comprise in the compound represented by formula (1) to formula (3) respectively any one or two or more time, larger effect can be obtained.In this case, when meeting 0<f≤1.5 and 0≤h<1 in formula (2), even larger effect can be obtained.
In addition, when silyl compound comprises the compound represented by formula (4), more specifically, by formula (4-1) to (4-17) each represent compound in any one or two or more time, even larger effect can be obtained.In this case, when the content of the silyl compound in electrolyte is 0.01wt% to 3wt%, even larger effect can be obtained.
1-2, laminated membrane type
Fig. 3 shows the perspective view of the decomposition configuration of another secondary cell of this implementer formula and Fig. 4 is zoomed-in view along the cross section that the IV-IV line of the rolled electrode bodies 30 shown in Fig. 3 intercepts.Hereinafter, the element of above-mentioned cylinder type secondary battery will frequently be quoted.
The configured in one piece of secondary cell
Secondary cell described here can be such as so-called laminated membrane type lithium rechargeable battery.
In the secondary battery, such as, as shown in Figure 3 and Figure 4, rolled electrode bodies 30 is stored in membranaceous external member 40.Carry out lamination through barrier film 35 and dielectric substrate 36 pairs of positive poles 33 and negative pole 34, the layered product obtained that reels subsequently is to form rolled electrode bodies 30.Positive wire 31 is connected to positive pole 33, and negative wire 32 is connected to negative pole 34.The outermost perimembranous of rolled electrode bodies 30 is protected by boundary belt 37.
Positive wire 31 and negative wire 32 such as can lead to outside from the inside of external member 40 in the same direction.Positive wire 31 is such as by any one in electric conducting material or two or morely to make as aluminium.Negative wire 32 is such as by any one in electric conducting material or two or morely to make as copper, nickel and stainless steel.These electric conducting materials are such as lamellar or netted.
External member 40 is such as a slice film, and it can fold along the direction of the arrow R shown in Fig. 3 and in a part for external member 40, arrange the ducted body for storing rolled electrode bodies 30.External member 40 is such as the laminated film of wherein such as lamination melting layer, metal level and sealer successively.In the manufacture process of secondary cell, by external member 40 folding make melting layer through rolled electrode bodies 30 toward each other after, the external edge edge of melting layer can be melt bonded.But external member 40 can by being formed in conjunction with two panels laminated film via adhesive etc.Melting layer is such as any one or the multiple film made in polyethylene, polypropylene etc.Metal layer in this way in aluminium foil etc. any one or two or more.Sealer is such as any one or the two or more film made in nylon, PETG etc.
Wherein, the external member 40 preferably wherein lamination aluminium lamination press mold of polyethylene film, aluminium foil and nylon membrane successively.But external member 40 can be the laminated film with other laminar structures, can be polymer film as polypropylene, can be maybe metal film.
The bonding film 41 being used for preventing extraneous air from entering is inserted between external member 40 and positive wire 31, negative wire 32.Bonding film 41 is made up of material positive wire 31 and negative wire 32 to adhesion characteristics.The example with the material of adhesion characteristics can comprise as any one in the vistanexes such as polyethylene, polypropylene, modified poly ethylene and modified polypropene or multiple.
Positive pole 33 such as has positive electrode active material layer 33B on a surface or two surfaces of positive electrode collector 33A, and negative pole 34 such as has anode active material layer 34B on negative electrode collector 34A surface or two surfaces.The configuration of positive electrode collector 33A, positive electrode active material layer 33B, negative electrode collector 34A and anode active material layer 34B is as identical with the configuration of anode active material layer 22B with positive electrode collector 21A, positive electrode active material layer 21B, negative electrode collector 22A respectively.The configuration of barrier film 35 is as identical with the configuration of barrier film 23.
Dielectric substrate 36 comprises electrolyte and macromolecular compound and electrolyte is kept by macromolecular compound.Dielectric substrate 36 is so-called gel electrolytes.Reason is that of obtaining high ion-conductivity (such as, being at room temperature more than 1mS/cm) and prevents the leak of liquid of electrolyte.Dielectric substrate 36 can comprise other materials such as additive further.
Macromolecular compound such as comprises polyacrylonitrile, polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene, poly(ethylene oxide), PPOX, polyphosphazene, polysiloxanes, polyvinyl fluoride, polyvinyl acetate, polyvinyl alcohol, polymethyl methacrylate, polyacrylic acid, polymethylacrylic acid, butadiene-styrene rubber, acrylonitrile-butadiene rubber, polystyrene, Merlon.In addition, macromolecular compound can be copolymer.The copolymer of copolymers vinylidene fluoride and hexafluoropropylene in this way.Wherein, be preferred and as copolymer vinylidene fluoride and hexafluoropropylene copolymer as homopolymers polyvinylidene fluoride be preferred.Reason is above-claimed cpd is electrochemical stability.
The composition of electrolyte is such as similar with the composition of the electrolyte of cylinder type secondary battery.But as in the dielectric substrate 36 of gel electrolyte, the term " solvent " of electrolyte represents that not only comprise liquid flux but also comprise can the broad concept with the material of ionic conductivity of dissociation electrolytic salt.Therefore, when use has the macromolecular compound of ionic conductivity, solvent also comprises macromolecular compound.
Here, can be used as it is electrolyte to replace gel electrolyte layer 36.In this case, electrolyte is immersed in rolled electrode bodies 30.
The operation of secondary cell
Secondary cell operates as follows.
When charging, when lithium ion discharges from positive pole 33, lithium ion is absorbed in negative pole 34 by dielectric substrate 36.On the other hand, when discharging, when lithium ion discharges from negative pole 34, lithium ion is absorbed in positive pole 33 by dielectric substrate 36.
The manufacture method of secondary cell
The secondary cell comprising gel electrolyte layer 36 such as manufactures by following three kinds of steps.
In a first step, by manufacturing positive pole 33 and negative pole 34 with positive pole 21 and the similar manufacturing step of negative pole 22.That is, when manufacturing positive pole 33, two surfaces of positive electrode collector 33A form positive electrode active material layer 33B, and when manufacturing negative pole 34, two surfaces of negative electrode collector 34A form anode active material layer 34B.Subsequently, precursor solution is prepared by mixed electrolytic solution, macromolecular compound, solvent etc.Described solvent is such as organic solvent etc.Subsequently, utilize precursor solution to be coated with positive pole 33 and negative pole 34, thus form gel electrolyte layer 36.Subsequently, by welding etc., positive wire 31 is connected to positive electrode collector 33A, and by welding etc., negative wire 32 is connected to negative electrode collector 34A.Subsequently, utilize barrier film 35 therebetween, positive pole 33 and negative pole 34 are carried out lamination and reeled, to form rolled electrode bodies 30.Then, boundary belt 37 is adhered to its outermost perimembranous.Subsequently, after rolled electrode bodies 30 being inserted between the membranaceous external member 40 of two panels, by hot melt adhesive method etc., rolled electrode bodies 30 is encapsulated in external member 40 by the bonding of the outward flange of described external member 40.In this case, bonding film 41 is inserted into positive wire 31 and between negative wire 32 and external member 40.
In the second step, positive wire 31 is connected to positive pole 33, and negative wire 32 is connected to negative pole 34.Subsequently, utilize barrier film 35 pairs of positive poles 33 therebetween and negative pole 34 to carry out lamination, and reeled to form the coiling body as the precursor of rolled electrode bodies 30.Then, boundary belt 37 is adhered to its outermost perimembranous.Subsequently, after coiling body being inserted between the membranaceous external member 40 of two panels, by hot melt adhesive method etc. by except except most peripheral bonding to obtain bag shape state, and coiling body to be contained in bag-shaped external member 40.Subsequently, preparation comprises electrolyte, monomer, polymerization initiator and other materials as the raw material for macromolecular compound as the composition of polymerization inhibitor (if needs), will be used for electrolytical composition and be injected in bag-shaped external member 40.Afterwards, by hot melt adhesive method etc., external member 40 is sealed airtightly.Subsequently, by monomer thermal polymerization, macromolecular compound is formed thus.Thus, gel electrolyte layer 36 is formed.
In third step, form coiling body in the mode similar with above-mentioned second step and be contained in bag-shaped external member 40, difference is, uses two sided coatings to have the barrier film 35 of macromolecular compound.The example being coated with the macromolecular compound of cloth diaphragm 35 can comprise and comprise the polymer (homopolymers, copolymer, multiple copolymer etc.) of vinylidene fluoride as composition.Its instantiation can comprise polyvinylidene fluoride, containing vinylidene fluoride and hexafluoropropylene as composition bipolymer, comprise vinylidene fluoride, hexafluoropropylene and the chlorotrifluoroethylene terpolymer as composition.It should be noted that except comprising vinylidene fluoride as except the polymer of composition, other one or more macromolecular compounds can also be used.Subsequently, prepared electrolyte and be injected in external member 40.Then, by hot melt adhesive method etc., the opening of external member 40 is hermetic sealed.Subsequently, while weight is applied to external member 40, gains are heated, and utilize macromolecular compound therebetween that barrier film 35 is attached to positive pole 33 and negative pole 34.Thus, utilize electrolyte to flood macromolecular compound, and therefore by macromolecular compound gelation to form dielectric substrate 36.
In third step, further suppress the expansion of secondary cell compared with first step.In addition, in third step, compared with second step, monomer, solvent etc. as the raw material of macromolecular compound not easily remain in dielectric substrate 36.Thus, the forming step of macromolecular compound is advantageously controlled.Therefore, adhere fully at positive pole 33, negative pole 34 and barrier film 35 and dielectric substrate 36.
The operation of secondary cell and effect
According to laminated membrane type secondary cell, because positive pole 33 comprises specific lithium-containing compound and dielectric substrate 36 (electrolyte) comprises silyl compound, therefore excellent battery behavior can be obtained for the reason identical with cylinder type secondary battery.In addition operation is identical with effect with the operation of cylinder type secondary battery with effect.
2, the application of secondary cell
Then, description is provided by the application examples of above-mentioned secondary cell.
The application of secondary cell is not particularly limited, as long as secondary cell is applicable to be allowed to use described secondary cell as driving power, machine, equipment, instrument, device, system (aggregate entities etc. of multiple equipment etc.) for the power storage source etc. of power storage.The secondary cell that secondary cell is used as power supply can be main power source (the preferential power supply used), can be maybe accessory power supply (power supply that replacement main power source uses, or the power supply used by switching from main power source).When secondary cell is used as accessory power supply, main power source type is not limited to secondary cell.
The application examples of secondary cell is as described below.These are electronic equipment (comprising portable electric appts) such as video camera, digital camera, mobile phone, notebook-sized personal computer, cordless telephone, stereophone, portable radio, portable television and portable data assistances.Other are applied as movable living electrical equipment such as electric shaver; Holder equipment such as stand-by power supply and memory card; Electric tool such as electric drill and electric saw; For notebook-sized personal computer etc. as connecting the battery pack with detachable power source; Medical electric device such as pacemaker and hearing aids; Motor vehicle is electric automobile (comprising hybrid vehicle) such as; And electric power storage system is such as storing the household batteries system etc. of emergence power.Much less, other application except above-mentioned application can be had.
Wherein, secondary cell can effectively for the application of such as battery pack, motor vehicle, electric power storage system, electric tool and electronic installation etc.Such a reason is, in such applications, owing to needing excellent battery behavior, so effectively can improve characteristic by using according to the secondary cell of this implementer formula.It should be noted that battery pack is the power supply using secondary cell, and be so-called assembled battery.Motor vehicle is the vehicle using secondary cell to carry out work (running) as driving power.As mentioned above, motor vehicle can be the automobile (such as hybrid vehicle) of other drive sources comprised except secondary cell.Electric power storage system uses secondary cell as the system in power storage source.Such as, in household power stocking system, owing to storing electric power in the secondary cell as power storage source, therefore use electric power, thus, domestic electronic appliances etc. become available.Electric tool is the instrument being moved movable part (such as drill bit) by use secondary cell as driving power.Electronic equipment is the equipment being performed various function by use secondary cell as driving power (supply of electric power source).
Here, the description of some application examples of secondary cell will specifically be provided.Here, the configuration of each application examples described below is only example and can suitably revises.
2-1, battery pack (single battery)
Fig. 5 represents the perspective configuration of the battery pack of use single battery and Fig. 6 represents that the square frame of the battery pack shown in Fig. 5 configures.Here, Fig. 5 shows the state that battery pack is disassembled.
Battery pack described herein is use secondary cell (so-called Soft Roll (soft pack)) and the simple battery pack be such as arranged on smart mobile phone on the electronic equipment being representative.Battery pack is such as provided with power supply 111 and circuit board 116, and described power supply is laminated membrane type secondary cell, and described circuit board is connected with the power supply 111 shown in Fig. 5.Positive wire 112 and negative wire 113 are connected to power supply 111.
A pair adhesive tape 118 and 119 is attached to two side surfaces of power supply 111.Protective circuit (PCM: protective circuit module) is formed in circuit board 116.Circuit board 116 to be connected with positive wire 112 via auricle (tab) 114 and to be connected with negative wire 113 via auricle 115.In addition, circuit board 116 connects with the lead-in wire 117 with the connector be connected for outside.Here, under the state that circuit board 116 is connected with power supply 111, circuit board 116 is protected at top and bottom by label 120 and insulating trip 121.Circuit board 116, insulating trip 121 etc. are fixed by attachment label 120.
In addition, battery pack is such as provided with power supply 111 as shown in Figure 6 and circuit board 116.Circuit board 116 is such as provided with control part 121, switching part 122, PTC 123 and temperature detecting part 124.Because power supply 111 can be connected with outside with negative terminal 127 via positive terminal 125, therefore power supply 111 is via positive terminal 125 and negative terminal 127 discharge and recharge.Temperature detecting part 124 can carry out detected temperatures by serviceability temperature detection terminal (so-called T terminal) 126.
Control part 121 controls the operation of whole battery pack (it comprises the using state of power supply 111) and comprises such as CPU (CPU), memory etc.
Such as, when cell voltage reaches overload detection voltage, control part 121 prevents charging current from flowing into the current path of power supply 111 by disconnecting switching part 122.In addition, such as, when big current flows between charge period, control part 121 interrupts charging current by disconnecting switching part 122.
In addition, such as, when cell voltage reaches overdischarge detection voltage, control part 121 prevents discharging current from flowing into the current path of power supply 111 by disconnecting switching part 122.In addition, such as, when big current flows at interdischarge interval, control part 121 interrupts discharging current by disconnecting switching part 122.
Here, secondary cell overcharge detect voltage be such as 4.20V ± 0.05V and overdischarge detect voltage be such as 2.4V ± 0.1V.
Switching part 122 carrys out the using state (whether can connect voltage 111 and external equipment) of Switching power 111 according to the instruction of control part 121.Switching part 122 such as comprises charging control switch, discharge control switch etc.Each of charging control switch and discharge control switch is such as semiconductor switch such as MOS (metal-oxide-semiconductor) memory (MOSFET).Here, charging and discharging currents such as detects based on the ON resistance of switching part 122.
Temperature detecting part 124 is measured the temperature of power supply 111 and is exported measurement result to control part 121, and comprises such as detector unit such as thermistor.Here, when control part 121 at abnormal heating time perform charge and discharge control, when control part 121 calculate residual capacity time perform trimming process, the measurement result of serviceability temperature test section 124.
Here, circuit board 116 is not necessarily provided with PTC 123.In this case, PTC element can be provided in separately in circuit board 116.
2-2, battery pack (assembled battery)
Fig. 7 represents the square frame configuration of the battery pack using assembled battery.Battery pack is such as provided with control part 61, power supply 62, switching part 63, current measurement portion 64, temperature detecting part 65, voltage detection department 66, switching controlling part 67, memory 68, temperature-detecting device 69, current sense resistor 70, positive terminal 71 and negative terminal 72 in the housing 60 be made up of plastic material etc.
Control part 61 controls the operation (comprising the using state of power supply 62) of whole battery pack and can comprise such as CPU etc.Power supply 62 comprises one or more secondary cell (not shown).Power supply 62 can be the assembled battery such as comprising two or more secondary cell.The connection type of these secondary cells can be connected in series type, can be the type of being connected in parallel, or its mixed type.As an example, power supply 62 comprises six secondary cells be connected with the mode of three series connection with two parallel connections.
Switching part 63 is according to the operation (whether power supply 62 can be connected to external equipment) of the instruction Switching power 62 of control part 61.Switching part 63 can comprise the (not shown) such as such as charging control switch, discharge control switch, charging diode, discharge diode.Charging control switch and discharge control switch can be the field-effect transistor (MOSFET) that such as semiconductor switch such as uses metal-oxide semiconductor (MOS).
Current measurement portion 64 uses current sense resistor 70 to measure electric current and to export measurement result to control part 61.Temperature detecting part 65 serviceability temperature checkout gear 69 carrys out measuring tempeature and exports measurement result to control part 61.Temperature measurement result may be used for such as wherein control part 61 control when abnormal heat generation discharge and recharge situation or wherein when calculating residual capacity control part 61 carry out the situation of correction process.Voltage detection department 66 measures the voltage of the secondary cell in power supply 62, carries out analog to digital conversion, and acquired results is supplied to control part 61 to the voltage measured.
Switching controlling part 67 is according to the operation of the signal controlling switching part 63 inputted from current measurement portion 64 and voltage detection department 66.
When such as cell voltage reaches overcharge detection voltage, switching controlling part 67 performs control, makes to prevent charging current from flowing in the current path of power supply 62 by disconnecting switching part 63 (charging control switch).Thus, in power supply 62, only allow to perform electric discharge by discharge diode.Here, such as, when flowing through big current when charging, switching controlling part 67 interrupts charging current.
In addition, such as, when cell voltage reaches overdischarge detection voltage, switching controlling part 67 performs control, makes to prevent discharging current from flowing in the current path of power supply 62 by disconnecting switching part 63 (discharge control switch).Thus, in power supply 62, only allow to perform charging by charging diode.Here, such as, when flowing through big current when discharging, switching controlling part 67 interrupts discharging current.
Here, in the secondary battery, such as, overcharge detect voltage be 4.20V ± 0.05V and overdischarge detect voltage be 2.4V ± 0.1V.
Memory 68 is that such as memory is as the EEPROM etc. as nonvolatile memory.Memory 68 can store the information (internal resistance under such as initial condition) of the numerical value such as calculated by control part 61 and the secondary cell recorded in manufacturing step.It should be noted that when memory 68 stores the complete charging capacity of secondary cell, allow control part 10 to obtain the information of such as residual capacity.
Detector unit 69 is measured the temperature of power supply 62 and is exported measurement result to control part 61.Detector unit 69 is such as thermistors etc.
Positive terminal 71 and negative terminal 72 be connected to use battery driven external equipment (such as, notebook-sized personal computer) terminal, or be connected to the terminal of the external equipment (such as, battery charger) for charging to battery pack.Discharge and recharge is carried out by positive terminal 71 and negative terminal 72 pairs of power supplys 62.
2-3, motor vehicle
Fig. 8 shows the square frame configuration of the hybrid vehicle of the example as motor vehicle.Such as, motor vehicle can comprise control part 74, engine 75, power supply 76, CD-ROM drive motor 77, differential mechanism 78, generator 79, transmission device 80, clutch 81, inverter 82 and 83 and various transducer 84 at the housing 73 be made of metal.In addition, motor vehicle can comprise the front wheel driving shaft 85 and front-wheel 86, rear wheel driving axle 87 and trailing wheel 88 that are such as connected to differential mechanism 78 and transmission device 80.
Motor vehicle can use such as one of engine 75 and motor 77 to operate as drive source.Engine 75 is main power sources, and can be such as petrol engine.When engine 75 is used as power source, can by the actuating force (rotatory force) of engine 75 such as being transferred to front-wheel 86 or trailing wheel 88 as the differential mechanism 78 of drive division, transmission device 80 and clutch 81.The rotatory force of engine 75 can also be transferred to generator 79.Due to rotatory force, generator 79 produces alternating electromotive force.By inverter 83, alternating electromotive force is converted to direct current power, by the power storage changed thus in power supply 76.On the contrary, when using when being used as power source as the motor 77 of converter section, by inverter 82, the electric power supplied from power supply 76 (direct current power) is converted into alternating electromotive force.CD-ROM drive motor 77 can be carried out by alternating electromotive force.Can by the actuating force (rotatory force) by utilizing motor 77 power conversion to obtain such as being transferred to front-wheel 86 or trailing wheel 88 as the differential mechanism 78 of drive division, transmission device 80 and clutch 81.
Here, when reducing the speed of motor vehicle by unshowned brake mechanism, resistance when speed being reduced transfers to motor 77 as rotatory force, and described motor 77 produces alternating electromotive force by rotatory force.Can preferably, by inverter 82 alternating electromotive force is converted into direct current power and the direct current power of regeneration is stored in power supply 76.
Control part 74 controls the operation of whole motor vehicle, and such as comprises CPU etc.Power supply 76 comprises one or more secondary cell (not shown).Selectively, power supply 76 can be connected to external power source, and can store electric power by receiving electric power from external power source.Various transducer 84 can be used for such as controlling the number of revolutions of engine 75 or being used for controlling the level of opening (level is opened in throttling) of unshowned choke valve.Various transducer 84 comprises such as velocity transducer, acceleration transducer and engine frequencies sensor.
Here, the description of the hybrid vehicle as motor vehicle has been given.But motor vehicle can be the vehicle (electric automobile) only using power supply 76 and motor 77 and do not use engine 75 and work.
2-4, electric power storage system
Fig. 9 shows the square frame configuration of electric power storage system.Such as, electric power storage system can house 89 as the inside of house and commercial building comprise control part 90, power supply 91, intelligent instrument 92 and power hub (power hub, electric power hub) 93.
Here, such as, power supply 91 is connected to the electric equipment 94 being arranged on inside, house 89, and can be connected to the motor vehicle 96 being parked in outside, house 89.In addition, such as, power supply 91 can be connected to by power hub 93 private power generator 95 be arranged in house 89, and can be connected to outside concentrated electric power system 97 by intelligent instrument 92 and power hub 93.
Here, electric equipment 94 comprises such as one or more household electrical appliance such as refrigerator, air-conditioning, TV and water heater.Private power generator 95 can be in such as solar generator and wind-driven generator etc. any one or multiple.Motor vehicle 96 can be one or more in such as electric automobile, battery-operated motor cycle and hybrid vehicle etc.Concentrate electric power system 97 can be one or more in such as Thermal Power Station, atomic power plant, hydraulic power plant and wind power plant etc.
Control part 90 controls the operation (comprising the operation of power supply 91) of whole electric power storage system, and can comprise such as CPU etc.Power supply 91 comprises one or more secondary cell (not shown).Intelligent instrument 92 can be such as with the electricity meters of Web-compatible of inside, house 89 being arranged on electricity consumer, and can be communicated with electric supply.Therefore, such as, while intelligent instrument 92 with ft connection, intelligent instrument 92 controls the balance between the supply and demand in house 89, and allows effective and stable energy supply.
In electric power storage system, such as, by intelligent instrument 92 and power hub 93, electric power can be stored in power supply 91 from the concentrated electric power system 97 as external power source, and can by power hub 93 from the private power generator 95 as independent current source by power storage power supply 91.Electric equipment 94 or motor vehicle 96 is supplied power to being stored in power supply 91 according to the instruction of control part 90.Therefore, electric equipment 94 becomes and can operate, and motor vehicle 96 becomes chargeable.That is, electric power storage system makes it possible to store in house 89 with power supply 91 and supply the system of electric power.
The electric power stored in power supply 91 is available arbitrarily.Therefore, such as, the midnight when electricity price is cheap electric power can be stored in power supply 91 from concentrated electric power system 97, and the electric power be stored in power supply 91 can be used during the daytime when electricity price is expensive.
Here, above-mentioned electric power storage system can be set to each house (each family), or above-mentioned electric power storage system can be set to multiple house (multiple family).
2-5, electric tool
Figure 10 shows the square frame configuration of electric tool.Such as, electric tool can be electric drill and can comprise such as control part 99 and power supply 100 at the tool body 98 be made up of plastic material etc.Such as, in the mode that can operate (rotatable), the bit part 101 as movable part is attached on tool body 98.
Control part 99 controls the operation (comprising the using state of power supply 100) of whole electric tool, and comprises such as CPU etc.Power supply 100 comprises one or more secondary cell (not shown).Electric power, according to the operation of unshowned console switch, is supplied to bit part 101 from power supply 100 by control part 99.
Embodiment
Specific embodiment according to this implementer formula will be described in detail.
Experimental example 1-1 to 1-21
Laminated membrane type lithium rechargeable battery shown in Fig. 3 and Fig. 4 manufactures according to following steps.
When manufacturing positive pole 33, first, the positive conductive agent (graphite) of the positive electrode binder (polyvinylidene fluoride) of the positive active material of 91 mass parts, 3 mass parts and 6 mass parts is mixed to form cathode mix.First lithium-containing compound (Li 1.15(Mn 0.65ni 0.22co 0.13) 0.85o 2) be used as positive active material.Subsequently, cathode mix is dispersed in organic solvent (METHYLPYRROLIDONE) to form cathode mix slurry.Then, after on two surfaces cathode mix slurry being evenly coated in strip positive electrode collector 33A (thickness is the aluminium foil of 12 μm), positive electrode active material layer 33B is formed by dry cathode mix slurry.Finally, by roll squeezer by compressing for positive electrode active material layer 53B.
When manufacturing negative pole 34, first, the negative electrode binder (polyvinylidene fluoride) of the negative electrode active material of 90 mass parts and 10 mass parts is mixed to form negative electrode mix.Material with carbon element (graphite) is used as negative electrode active material.Subsequently, negative electrode mix is dispersed in organic solvent (METHYLPYRROLIDONE) to form negative electrode mix slurry.Then, after on two surfaces negative electrode mix slurry being evenly coated in strip negative electrode collector 34A (thickness is the aluminium foil of 15 μm), negative electrode active material layer 34B is formed by dry negative electrode mix slurry.Finally, by roll squeezer by compressing for negative electrode active material layer 34B.
When preparing liquid electrolyte (electrolyte), by electrolytic salt (LiPF 6) be dissolved in mixed solvent (ethylene carbonate and methyl ethyl carbonate) and prepare mixed solution.In this case, the composition of mixed solvent is set to ethylene carbonate with weight ratio: methyl ethyl carbonate=35:65 and electrolytic salt is set to 1.2mol/dm relative to the content of mixed solvent 3(=1mol/l).Subsequently, after being added in mixed solution by silyl compound, solution is uniformly mixed as required.The type of silyl compound and content (wt%) as shown in table 1.
When secondary cell for assembling, first, positive wire 25 made of aluminum is soldered to positive pole 33 (positive electrode collector 33A), and the negative wire 26 be made of copper is soldered to negative pole 34 (negative electrode collector 34A).Subsequently, after via barrier film 35 (thickness is the polyethylene film of 20 μm) lamination positive pole 33 and negative pole 34, by welding manufacture rolled electrode bodies 30 in a longitudinal direction, outmost to boundary belt 37 and its outer part is combined.Subsequently, make external member 40 bending with after inserting rolled electrode bodies 30, the peripheral edge portion on three sides of external member 40 is heated and is fused together.Thus, rolled electrode bodies 30 is stored in inside bag-shaped external member 40.External member 40 to be thickness be nylon membrane, the thickness of 25 μm the is aluminium foil of 40 μm and thickness are the moistureproof aluminium lamination press mold of the polypropylene screen of the 30 μm lamination successively from outside.Finally, being noted by electrolyte, people is inner and after being impregnated into by electrolyte in barrier film 35 at external member 40, heats and fuse the residue side of external member 40 under reduced pressure atmosphere.In this case, adhesive film 41 (thickness is the sour modified propylene film of 50 μm) is inserted in positive wire 31 and between negative wire 32 and external member 40.
When checking battery behavior (cycle characteristics) of secondary cell, obtain as shown by the results in tablei.
When checking cycle characteristics, first, under normal temperature environment (23 DEG C), 1 charging and discharging circulation is implemented to stablize its battery status to secondary cell.Subsequently, another charging and discharging circulation is carried out at the same temperature to measure the discharge capacity in the 2nd circulation.Subsequently, by the same temperature to charging/discharging of secondary cell until circulation ading up to 100 times circulation measure the 100 time circulation discharge capacity.Capability retention (%)=(discharge capacity in the discharge capacity/2nd time circulation the 100th circulation) × 100 are calculated from this result.Between charge period, utilizing the current charges of 0.2C until cell voltage reaches specific voltage (upper voltage limit), with identical voltage to secondary cell charge until current density reaches 0.05C.At interdischarge interval, with the electric current of 0.2C, secondary cell is discharged until cell voltage reaches specific voltage (lower voltage limit).Each value of upper voltage limit and lower voltage limit is as shown in table 1.Here, " 0.2C " is the current value of the electric discharge completing battery capacity (theoretical capacity) in 5 hours, and " 0.05C " is the current value of the electric discharge completing battery capacity (theoretical capacity) in 20 hours.
Table 1
Electrolyte=electrolyte, upper voltage limit=4.55V, lower voltage limit=2V
To the charging/discharging of secondary cell of use first lithium-containing compound as positive active material under high charge voltage conditions.In this case, when electrolyte comprises silyl compound (experimental example 1-1 to 1-20), compared with the situation (experimental example 1-21) not comprising silyl compound with electrolyte, capability retention increases greatly, and does not depend on the type of silyl compound.
Especially, when the content of the silyl compound in electrolyte is 0.01wt% to 3wt%, sufficiently high capability retention can be obtained.
Experimental example 2-1 to 2-21 and 3-1 to 3-21
As shown in table 2 and table 3, except changing the kind of negative electrode active material, manufacture secondary cell according to same steps and check battery behavior.
When manufacturing negative pole 34, first, by mixing the cathode conductive agent (graphite) of the negative electrode active material of 90 mass parts, the material (polyamic acid (polyamicacid) as the precursor of polyimides) of the adhesive of 5 mass parts and 5 mass parts to form negative electrode mix.As silicon and the Antaciron (FeSi of metal based material 2) be used as negative electrode active material.Silica flour and ferro-silicon alloy powder average grain diameter separately (median diameter D50) is 5 μm.Subsequently, negative electrode mix is dispersed in organic solvent (METHYLPYRROLIDONE) to form negative electrode mix slurry.Subsequently, after on two surfaces negative electrode mix slurry being evenly coated in strip negative electrode collector 34A (thickness is the Copper Foil of 15 μm), mixture layer is formed by dry negative electrode mix slurry.Subsequently, by roll squeezer, mixture is compressing.Finally, under vacuum atmosphere, heat mixture layer (400 DEG C × 12 hours).Thus, owing to defining negative electrode binder (polyimides), because which form negative electrode active material layer 34B.
Table 2
Electrolyte=electrolyte, upper voltage limit=4.55V, lower voltage limit=2V
Table 3
Electrolyte=electrolyte, upper voltage limit=4.55V, lower voltage limit=2V
At use metal based material as (table 2 and table 3) when negative electrode active material, the result that same acquisition is identical with using the situation of material with carbon element (table 1).That is, under the condition of high charge voltage to the charging/discharging of secondary cell of use first lithium-containing compound as positive active material when, when electrolyte comprises silyl compound, capability retention increases greatly.
Experimental example 4-1 to 4-21,5-1 to 5-21, and 6-1 to 6-21
As shown in table 4 to table 6, except change electrolytical type except, according to same steps manufacture secondary cell and check battery behavior.
When forming gel-like electrolyte (dielectric substrate 36), first, by electrolytic salt (LiPF 6) be dissolved in mixed solvent (ethylene carbonate and propylene carbonate) to prepare colloidal sol (zol) shape mixed solution.In this case, the weight ratio of the composition of mixed solvent is set to ethylene carbonate: electrolytic salt is also set to 1mol/kg relative to the content of mixed solvent by methyl ethyl carbonate=50:50.Subsequently, as shown in table 4 to table 6, after adding in mixed solution by silyl compound, be uniformly mixed solution as required.Subsequently, the organic solvent (dimethyl carbonate) of the electrolyte of 30 mass parts, the macromolecular compound (copolymer of vinylidene fluoride and hexafluoropropylene) of 10 mass parts and 60 mass parts is mixed to prepare precursor solution.In copolymer, the copolymerization amount of hexafluoropropylene is 6.9wt%.Finally, after on each two surfaces precursor solution being coated in positive pole 33 and negative pole 34, dry precursor solution.Thus, gel-like electrolyte layer 36 is formed.
Table 4
Electrolyte=electrolyte layers, upper voltage limit=4.55V, lower voltage limit=2V
Table 5
Electrolyte=electrolyte layers, upper voltage limit=4.55V, lower voltage limit=2V
Table 6
Electrolyte=electrolyte layers, upper voltage limit=4.55V, lower voltage limit=2V
Equally when using gel-like electrolyte (electrolyte layers 36) (table 4 is to table 6), the result (table 1 to table 3) identical with using the situation of liquid electrolyte (electrolyte) can be obtained.That is, under the condition of high charge voltage to the charging/discharging of secondary cell of use first lithium-containing compound as positive active material when, when electrolyte comprises silyl compound, capability retention increases greatly.
Experimental example 7-1 to 7-18,8-1 to 8-18,9-1 to 9-18,10-1 to 10-18,11-1 to 11-18, and 12-1 to 12-18
As shown in table 7 to table 12, except changing the type of positive active material, manufacture secondary cell according to same steps and check battery behavior.Second lithium-containing compound (LiCoO 2with Li (Ni 0.5co 0.2mn 0.3) O 2) and the 3rd lithium-containing compound (NiMn 1.5ni 0.5o 4) be used as positive active material.
Table 7
Electrolyte=electrolyte, upper voltage limit=4.5V, lower voltage limit=3V
Table 8
Electrolyte=electrolyte, upper voltage limit=4.5V, lower voltage limit=3V
Table 9
Electrolyte=electrolyte, upper voltage limit=4.95V, lower voltage limit=3V
Table 10
Electrolyte=electrolyte layers, upper voltage limit=4.5V, lower voltage limit=3V
Table 11
Electrolyte=electrolyte layers, upper voltage limit=4.5V, lower voltage limit=3V
Table 12
Electrolyte=electrolyte layers, upper voltage limit=4.95V, lower voltage limit=3V
To (table 7 is to table 12) when charging/discharging of secondary cell as positive active material of use second lithium-containing compound and the 3rd lithium-containing compound under the condition of high charge voltage, the result identical with the situation using the first lithium-containing compound (table 1 is to table 6) can be obtained.That is, when electrolyte comprises silyl compound, capability retention increases greatly.
Experimental example 13-1 to 13-18,14-1 to 14-18,15-1 to 15-18, and 16-1 to 16-18
As shown in table 13 to table 16, the material except using specific lithium-containing compound, as outside positive active material, manufactures secondary cell according to same steps and checks battery behavior.Lithium transition metal phosphates compound (LiFePO 4) and lithium-transition metal composite oxide (LiMn 2o 4) be used as described other materials.
Table 13
Electrolyte=electrolyte, upper voltage limit=3.6V, lower voltage limit=2V
Table 14
Electrolyte=electrolyte, upper voltage limit=4.2V, lower voltage limit=3V
Table 15
Electrolyte=electrolyte layers, upper voltage limit=3.6V, lower voltage limit=2V
Table 16
Electrolyte=electrolyte layers, upper voltage limit=4.2V, lower voltage limit=3V
To (table 13 is to table 16) when the charging/discharging of secondary cell using another kind of material as positive active material under the condition of high charge voltage, obtain and results different to the situation using specific lithium-containing compound as the charging/discharging of secondary cell of positive active material (table 1 is to table 12) under the condition of high charge voltage.Particularly, when using another kind of material as positive active material, when under high charge voltage conditions to charging/discharging of secondary cell time, capability retention only according to whether there is silyl compound in electrolyte increases little by little, and capability retention reduces in some cases.
Experimental example 17-1 to 17-18 and 18-1 to 18-18
As shown in table 17 and table 18, remove under low charging voltage condition the specific lithium-containing compound (LiCoO of use 2) as outside the charging/discharging of secondary cell of positive active material, manufacture secondary cell according to same steps and check battery behavior.
Table 17
Electrolyte=electrolyte, upper voltage limit=4.2V, lower voltage limit=3V
Table 18
Electrolyte=electrolyte layers, upper voltage limit=4.2V, lower voltage limit=3V
Under low charging voltage condition, (table 17 and table 18) when the charging/discharging of secondary cell using specific lithium-containing compound as positive active material is obtained and results different to the situation using specific lithium-containing compound as the charging/discharging of secondary cell of positive active material (table 1 is to table 12) under the condition of high charge voltage.Particularly, when under low charging voltage condition to charging/discharging of secondary cell, capability retention only according to whether there is silyl compound in electrolyte increases little by little, and capability retention in most of the cases reduces.
According to table 1 to the result of table 18, when positive pole comprises specific lithium-containing compound and electrolyte comprises silyl compound, improve cycle characteristics.Therefore, excellent battery behavior is obtained.
Hereinbefore, execution mode and embodiment is used to give the description of this technology.But this technology is not limited to the form described in execution mode and embodiment, and can have various distortion.
Such as, use battery structure be the situation of column type and laminated membrane type as an example and the situation using cell device to have winding-structure provides description as an example.But this technology is not limited thereto.When having another battery structure such as square, Coin shape, button-type etc. or when also there is another structural rate as laminar structure at cell device, the secondary cell of this technology can be applied in an identical manner.
In addition, such as, electrode reaction thing can be another the 1st race's element such as sodium (Na) and potassium (K), can be the 2nd race's element such as magnesium and calcium, can be maybe another light metal such as aluminium.Owing to can estimate that how the type of no matter electrode reaction thing is all by obtaining the effect of this technology, even if therefore also can obtain identical effect when the type change of electrode reaction thing.
Here, this technology also can adopt following configuration.
(1) secondary cell, comprising: positive pole; Negative pole; And nonaqueous electrolytic solution, wherein said positive pole is included in the electrode compound that more than 4.5V current potential (current potential to lithium) absorbs and discharges electrode reaction thing, and nonaqueous electrolytic solution comprises silyl compound, wherein one or two is above containing siloxy (SiR 3-O-: three R are any one in univalence hydrocarbyl and its halogeno-group respectively) with silicon beyond atomistic binding.
(2) secondary cell according to above-mentioned (1), wherein electrode compound comprises at least one in the compound represented by formula (1) to formula (3) respectively,
Li 1+a(Mn bCo cNi 1-b-c) 1-aM1 dO 2-e(1)
(wherein M1 is at least one (not comprising manganese (Mn), cobalt (Co) and nickel (Ni)) in the element of the 2nd race to the 15th race belonging to long period type periodic table, a to e meets 0<a<0.25,0.3≤b<0.7,0≤c<1-b, 0≤d≤1 and 0≤e≤1)
Li fNi 1-g-hMn gM2 hO 2-iX j(2)
(wherein M2 is at least one (not comprising nickel and manganese) in the element of the 2nd race to the 15th race belonging to long period type periodic table, X is at least one (not comprising oxygen (O)) belonged in the 16th race of long period type periodic table and the element of the 17th race, and f to j meets 0≤f≤1.5,0≤g≤1,0≤h≤1 ,-0.1≤i≤0.2 and 0≤j≤0.2)
LiM3 kMn 2-kO 4(3)
(wherein M3 is at least one (not comprising manganese) in the element of the 2nd race to the 15th race belonging to long period type periodic table, and k meets 0<k≤1.)
(3) secondary cell according to above-mentioned (2), each wherein in M1 and M3 comprises nickel, cobalt, magnesium (Mg), aluminium (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), zirconium (Zr), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), tungsten (W), at least one in silicon (Si) and barium (Ba), M2 comprises cobalt, magnesium, aluminium, boron, titanium, vanadium, chromium, iron, copper, zinc, zirconium, molybdenum, tin, calcium, strontium, tungsten, at least one in silicon and barium, and X comprises fluorine (F), chlorine (Cl), bromine (Br), with at least one in iodine (I).
(4) secondary cell according to above-mentioned (2) or (3), wherein f meets 0<f≤1.5, or h meets 0≤h<1.
(5) secondary cell according to any one of above-mentioned (1) to (4), atom wherein beyond silicon is any one atom in aluminium, boron, phosphorus (P), sulphur (S), carbon (C) and hydrogen (H), univalence hydrocarbyl is alkyl, any one group in alkenyl, alkynyl, cycloalkyl, aryl and its two or more monoradicals be bonded to, and halogeno-group comprises at least one in fluorine-based (-F), chloro (-Cl), bromo (-Br) and iodo (-I).
(6) secondary cell according to any one of above-mentioned (1) to (5), wherein silyl compound comprises the compound represented by formula (4),
(SiR1 3-O-) m-Y (4)
(wherein three R1 are any one in univalence hydrocarbyl and its halogeno-group respectively, and Y comprises aluminium, boron, phosphorus, sulphur, carbon, with the group of any one atom in hydrogen as composed atom, but, containing the ehter bond (-O-) in siloxy and the aluminium in Y, boron, phosphorus, sulphur, carbon, combine with any one atom in hydrogen, and m is the integer of more than 1.)
(7) secondary cell according to above-mentioned (6), wherein Y is any one group in the group represented by formula (4-21) to formula (4-31) respectively,
(wherein Z1 is halogen radical, Z2 and Z4 is any one in univalence hydrocarbyl and its halogeno-group, and Z3 is any one group in hydrogen base and halogeno-group, and Z5 is any one group in bivalent hydrocarbon radical and its halogeno-group, and n is the integer of more than 1.)
(8) secondary cell according to above-mentioned (7), wherein halogen radical is fluorine-based, chloro, bromo, with any one group in iodo, univalence hydrocarbyl is alkyl, alkenyl, alkynyl, cycloalkyl, aryl, and any one group in its two or more monoradicals be bonded to, bivalent hydrocarbon radical is alkylidene, alkylene group, alkynylene, cycloalkylidene, arlydene, any one group in the divalent group that two or more are bonded to it, and halogeno-group comprises fluorine-based, chloro, bromo, and at least one in iodo.
(9) secondary cell according to any one of above-mentioned (1) to (8), wherein silyl compound comprises at least one in the compound represented by formula (4-1) to formula (4-17) respectively,
(wherein-Me represents methyl, and-t-Bu represents the tert-butyl group)
(wherein-Me represents methyl, and-Et represents ethyl.)
(10) secondary cell according to any one of above-mentioned (1) to (9), the content of the silyl compound wherein in nonaqueous electrolytic solution is 0.01wt% to 3wt%.
(11) secondary cell according to any one of above-mentioned (1) to (10), it is lithium rechargeable battery.
(12) battery pack, comprising: according to the secondary cell according to any one of above-mentioned (1) to (11); Control the control part of the operation of secondary cell; And the switching part of the operation of secondary cell is switched according to the instruction of control part.
(13) motor vehicle, comprising: according to the secondary cell according to any one of above-mentioned (1) to (11); Electric power from secondary cell supply is converted to the converter section of actuating force; The drive division driven is carried out according to actuating force; And the control part of the operation of control secondary cell.
(14) power storage system, comprising: according to the secondary cell according to any one of above-mentioned (1) to (11); One or more electric equipment, electric power is supplied to described electric equipment from secondary cell; And control the control part from secondary cell, electric equipment being supplied to electric power.
(15) electric tool, comprising: according to the secondary cell according to any one of above-mentioned (1) to (11); And movable part, electric power is supplied to described movable part from secondary cell.
(16) electronic equipment, comprising: according to the secondary cell as supply of electric power source according to any one of above-mentioned (1) to (11).
It should be appreciated by those skilled in the art that and can carry out various amendment, combination, sub-portfolio and change according to design requirement and other factors, as long as it is within the scope of claims or its equivalents.

Claims (16)

1. a secondary cell, comprising:
Positive pole;
Negative pole; And
Nonaqueous electrolytic solution,
Wherein, the current potential that described positive pole is included in more than 4.5V absorbs and discharges the electrode compound of electrode reaction thing, and described current potential is the current potential to lithium, and
Described nonaqueous electrolytic solution comprises silyl compound, and in described silyl compound, one or more is containing siloxy SiR 3atomistic binding beyond-O-and silicon, wherein three R are any one in univalence hydrocarbyl and its halogeno-group respectively.
2. secondary cell according to claim 1,
Wherein, described electrode compound comprises at least one in the compound represented by formula (1) to formula (3) respectively,
Li 1+a(Mn bCo cNi 1-b-c) 1-aM1 dO 2-e(1)
Wherein, M1 is at least one in the element of the 2nd race to the 15th race belonging to long period type periodic table, but do not comprise manganese (Mn), cobalt (Co) and nickel (Ni), a to e meets 0<a<0.25,0.3≤b<0.7,0≤c<1-b, 0≤d≤1 and 0≤e≤1
Li fNi 1-g-hMn gM2 hO 2-iX j(2)
Wherein, M2 is at least one in the element of the 2nd race to the 15th race belonging to long period type periodic table, but do not comprise nickel and manganese, X belongs at least one in the 16th race of long period type periodic table and the element of the 17th race, but does not comprise oxygen (O), and f to j meets 0≤f≤1.5,0≤g≤1,0≤h≤1 ,-0.1≤i≤0.2 and 0≤j≤0.2
LiM3 kMn 2-kO 4(3)
Wherein, M3 is at least one in the element of the 2nd race to the 15th race belonging to long period type periodic table, but do not comprise manganese, and k meets 0<k≤1.
3. secondary cell according to claim 2,
Wherein, M1 and M3 comprises at least one in nickel, cobalt, magnesium (Mg), aluminium (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), zirconium (Zr), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), tungsten (W), silicon (Si) and barium (Ba) separately
M2 comprises at least one in cobalt, magnesium, aluminium, boron, titanium, vanadium, chromium, iron, copper, zinc, zirconium, molybdenum, tin, calcium, strontium, tungsten, silicon and barium, and
X comprises at least one in fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).
4. secondary cell according to claim 2,
Wherein, f meets 0<f≤1.5, or
H meets 0≤h<1.
5. secondary cell according to claim 1,
Wherein, the atom beyond described silicon is any one atom in aluminium, boron, phosphorus (P), sulphur (S), carbon (C) and hydrogen (H),
Described univalence hydrocarbyl is alkyl, any one group in alkenyl, alkynyl, cycloalkyl, aryl and its two or more monoradicals be bonded to, and
Described halogeno-group comprises at least one in fluorine-based (-F), chloro (-Cl), bromo (-Br) and iodo (-I).
6. secondary cell according to claim 1,
Wherein, described silyl compound comprises the compound represented by formula (4),
(SiR1 3-O-) m-Y (4)
Wherein, three R1 are any one in univalence hydrocarbyl and its halogeno-group respectively, Y comprises the group of any one atom in aluminium, boron, phosphorus, sulphur, carbon and hydrogen as composed atom, but be combined containing any one atom in the aluminium of ehter bond (-O-) in Y, boron, phosphorus, sulphur, carbon and the hydrogen in siloxy, and m is the integer of more than 1.
7. secondary cell according to claim 6,
Wherein, Y is any one group in the group represented by formula (4-21) to formula (4-31) respectively,
Wherein, Z1 is halogen radical, Z2 and Z4 is any one in univalence hydrocarbyl and its halogeno-group, and Z3 is any one group in hydrogen base and halogeno-group, and Z5 is any one group in bivalent hydrocarbon radical and its halogeno-group, and n is the integer of more than 1.
8. secondary cell according to claim 7,
Wherein, described halogen radical is any one group in fluorine-based, chloro, bromo and iodo,
Described univalence hydrocarbyl is alkyl, any one group in alkenyl, alkynyl, cycloalkyl, aryl and its two or more monoradicals be bonded to,
Described bivalent hydrocarbon radical is alkylidene, any one group in alkylene group, alkynylene, cycloalkylidene, arlydene and its two or more divalent groups be bonded to, and
Halogeno-group comprises at least one in fluorine-based, chloro, bromo and iodo.
9. secondary cell according to claim 1,
Wherein, described silyl compound comprises at least one in the compound represented by formula (4-1) to formula (4-17) respectively,
Wherein ,-Me represents methyl, and-t-Bu represents the tert-butyl group,
Wherein ,-Me represents methyl, and-Et represents ethyl.
10. secondary cell according to claim 1,
Wherein, the content of the described silyl compound in described nonaqueous electrolytic solution is 0.01wt% to 3wt%.
11. secondary cells according to claim 1, described secondary cell is lithium rechargeable battery.
12. 1 kinds of battery pack, comprising:
Secondary cell;
Control the control part of the operation of described secondary cell; And
The switching part of the operation of described secondary cell is switched according to the instruction of described control part,
Wherein, described secondary cell is provided with positive pole, negative pole and nonaqueous electrolytic solution,
The current potential that described positive pole is included in more than 4.5V absorbs and discharges the electrode compound of electrode reaction thing, and described current potential is the current potential to lithium, and
Described nonaqueous electrolytic solution comprises silyl compound, and in described silyl compound, one or more is containing siloxy SiR 3atomistic binding beyond-O-and silicon, wherein three R are any one in univalence hydrocarbyl and its halogeno-group respectively.
13. 1 kinds of motor vehicles, comprising:
Secondary cell;
The electric power supplied from described secondary cell is converted to the converter section of actuating force;
The drive division driven is carried out according to described actuating force; And
Control the control part of the operation of described secondary cell;
Wherein, described secondary cell is provided with positive pole, negative pole and nonaqueous electrolytic solution,
The current potential that described positive pole is included in more than 4.5V absorbs and discharges the electrode compound of electrode reaction thing, and described current potential is the current potential to lithium, and
Described nonaqueous electrolytic solution comprises silyl compound, and in described silyl compound, one or more is containing siloxy SiR 3atomistic binding beyond-O-and silicon, wherein three R are any one in univalence hydrocarbyl and its halogeno-group respectively.
14. 1 kinds of power storage systems, comprising:
Secondary cell;
From described secondary cell, it is supplied to one or more electric equipment of electric power; And
Control from the control part of described secondary cell for the supply of electric power of described electric equipment,
Wherein, described secondary cell is provided with positive pole, negative pole and nonaqueous electrolytic solution,
The current potential that described positive pole is included in more than 4.5V absorbs and discharges the electrode compound of electrode reaction thing, and described current potential is the current potential to lithium, and
Described nonaqueous electrolytic solution comprises silyl compound, and in described silyl compound, one or more is containing siloxy SiR 3atomistic binding beyond-O-and silicon, wherein three R are any one in univalence hydrocarbyl and its halogeno-group respectively.
15. 1 kinds of electric tools, comprising:
Secondary cell; And
From described secondary cell, it is supplied to the movable part of electric power,
Wherein, described secondary cell is provided with positive pole, negative pole and nonaqueous electrolytic solution,
The current potential that described positive pole is included in more than 4.5V absorbs and discharges the electrode compound of electrode reaction thing, and described current potential is the current potential to lithium, and
Described nonaqueous electrolytic solution comprises silyl compound, and in described silyl compound, one or more is containing siloxy SiR 3atomistic binding beyond-O-and silicon, wherein three R are any one in univalence hydrocarbyl and its halogeno-group respectively.
16. 1 kinds of electronic equipments, comprising:
As the secondary cell in supply of electric power source,
Wherein, described secondary cell is provided with positive pole, negative pole and nonaqueous electrolytic solution,
The current potential that described positive pole is included in more than 4.5V absorbs and discharges the electrode compound of electrode reaction thing, and described current potential is the current potential to lithium, and
Described nonaqueous electrolytic solution comprises silyl compound, and in described silyl compound, one or more is containing siloxy SiR 3atomistic binding beyond-O-and silicon, wherein three R are any one in univalence hydrocarbyl and its halogeno-group respectively.
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WO2019003776A1 (en) 2017-06-30 2019-01-03 ダイキン工業株式会社 Electrolytic solution, electrochemical device, secondary cell, and module
JP6904176B2 (en) * 2017-09-01 2021-07-14 トヨタ自動車株式会社 Rechargeable battery reuse method and rechargeable battery system
KR102488602B1 (en) * 2017-09-06 2023-01-12 삼성에스디아이 주식회사 Non-electrolyte for rechargeable lithium battery and rechargeable lithium battery including same
WO2019220764A1 (en) 2018-05-14 2019-11-21 ダイキン工業株式会社 Electrolyte, electrochemical device, lithium-ion secondary battery, and module
JP7404056B2 (en) * 2018-12-13 2023-12-25 三菱ケミカル株式会社 Non-aqueous electrolyte and non-aqueous electrolyte secondary battery
CN116438676A (en) * 2020-10-14 2023-07-14 赛昂能源有限公司 Electrolyte for reducing gas production

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1316791A (en) * 2000-04-04 2001-10-10 松下电器产业株式会社 Nonaqueous electrolyte battery and nonaqueous electrolyte
CN103490093A (en) * 2012-06-07 2014-01-01 索尼公司 Electrode, secondary battery, battery pack, electric vehicle and electric power storage system
CN103490095A (en) * 2012-06-11 2014-01-01 索尼公司 Electrolytic solution, secondary battery, battery pack, electric vehicle and electric power storage system

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5783333A (en) * 1996-11-27 1998-07-21 Polystor Corporation Lithium nickel cobalt oxides for positive electrodes
JP4183374B2 (en) * 2000-09-29 2008-11-19 三洋電機株式会社 Nonaqueous electrolyte secondary battery
EP1351327A4 (en) * 2000-11-20 2004-08-18 Chuo Denki Kogyo Co Ltd Nonaqueous electrolyte secondary cell and positive electrode active material
JP4984022B2 (en) * 2005-10-28 2012-07-25 ソニー株式会社 Secondary battery
US20120315534A1 (en) * 2011-06-09 2012-12-13 Wildcat Discovery Technologies, Inc. Materials for Battery Electrolytes and Methods for Use
KR101863094B1 (en) * 2011-09-16 2018-07-05 삼성에스디아이 주식회사 Composite cathode active material, and cathode and lithium battery containing the material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1316791A (en) * 2000-04-04 2001-10-10 松下电器产业株式会社 Nonaqueous electrolyte battery and nonaqueous electrolyte
CN103490093A (en) * 2012-06-07 2014-01-01 索尼公司 Electrode, secondary battery, battery pack, electric vehicle and electric power storage system
CN103490095A (en) * 2012-06-11 2014-01-01 索尼公司 Electrolytic solution, secondary battery, battery pack, electric vehicle and electric power storage system

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XIAOXI ZUO ETAL: ""Effect of tris(trimethylsilyl)borate on the high voltage capacity"", 《JOURNAL OF POWER SOURCES》 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105355968A (en) * 2015-11-24 2016-02-24 宁德新能源科技有限公司 Electrolyte and lithium ion battery inducing same
CN105355968B (en) * 2015-11-24 2019-01-08 宁德新能源科技有限公司 electrolyte and lithium ion battery including the electrolyte
CN108370064A (en) * 2015-12-04 2018-08-03 株式会社村田制作所 Secondary cell, battery pack, electric vehicle, electric power storage system, electric tool and electronic equipment
CN108370064B (en) * 2015-12-04 2021-10-29 株式会社村田制作所 Secondary battery, battery pack, electric vehicle, power storage system, electric power tool, and electronic device
CN108242557A (en) * 2016-12-26 2018-07-03 宁德时代新能源科技股份有限公司 Electrolyte solution and secondary battery
CN108242567A (en) * 2016-12-26 2018-07-03 宁德时代新能源科技股份有限公司 Electrolyte solution and secondary battery
CN108242557B (en) * 2016-12-26 2020-08-28 宁德时代新能源科技股份有限公司 Electrolyte solution and secondary battery
CN110720149A (en) * 2017-06-15 2020-01-21 株式会社村田制作所 Secondary battery, battery pack, electric vehicle, power storage system, electric power tool, and electronic device
US11424477B2 (en) 2017-06-15 2022-08-23 Murata Manufacturing Co., Ltd. Secondary battery, battery pack, electric vehicle, electric power storage system, electric power tool, and electronic apparatus
CN110495040A (en) * 2017-06-30 2019-11-22 大金工业株式会社 Electrolyte, electrochemical device, secondary cell and component
CN113921907A (en) * 2021-09-28 2022-01-11 湖南立方新能源科技有限责任公司 Additive for sodium ion battery electrolyte, electrolyte and sodium ion battery
CN113921907B (en) * 2021-09-28 2024-07-02 湖南钠方新能源科技有限责任公司 Additive for sodium ion battery electrolyte, electrolyte and sodium ion battery

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